WO1994023468A1 - Layer for stabilization of lithium anode - Google Patents
Layer for stabilization of lithium anode Download PDFInfo
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- WO1994023468A1 WO1994023468A1 PCT/US1994/002976 US9402976W WO9423468A1 WO 1994023468 A1 WO1994023468 A1 WO 1994023468A1 US 9402976 W US9402976 W US 9402976W WO 9423468 A1 WO9423468 A1 WO 9423468A1
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- polymer
- lithium
- negative electrode
- iodine
- poly
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- This invention relates to electrochemical batteries, and more particularly, to improved electrode and electrode-current collector assemblies for such batteries.
- lithium when used as the negative electrode, is attacked and/or passivated by electrolytes. This results in formation of lithium powder with a very high surface area at the interface between the metallic lithium and the electrolyte. The formation of high surface area lithium powder is undesirable because it reacts violently with moisture and air and results in degradation of cell performance.
- Lithium alloy active materials have a relatively short cycle life due to mechanical degradation of the electrode.
- an electrochemical cell which has a negative electrode which comprises a solid body comprising an active metal material preferably consisting of lithium metal or compounds thereof and having a major surface facing an electrolyte or an electrolyte separator; and a layer disposed between the major surface of the negative electrode and the electrolyte.
- the layer is a coating carried on the major surface of the negative electrode.
- the coating comprises an organic polymer material intermingled with iodine forming a polymer- iodine complex.
- the iodine is in ionic or particle form and dispersed with the polymer.
- the coating is a conductor of electrons and a conductor of the active metal ions (Li+) of the negative electrode.
- the coating is of a thickness sufficient to restrict penetration of electrolyte therethrough, while at the same time, conduct electrons and positive lithium ions.
- the organic polymer is polyvinyl pyridine
- PVP poly-2-vinylpyridine
- P2VP poly-2-vinylpyridine
- the anode coating of the invention is useful for protecting metallic lithium anodes in batteries having cathodes which do not include iodine as an active material.
- Preferred cathode active materials include transition metal chalcogen compound having a reversible lithium insertion ability, wherein the transition metal is at least one selected from the group consisting of Ti, V, Cr, Mn, Fe, Nb, Mo, Ta and , and the chalcogen is at least one selected from the group consisting of 0, S and Se. Accordingly, it is an object of the present invention to provide an improved electrochemical battery based on lithium which maintains its integrity over a prolonged life-cycle as compared to presently used batteries. Another object is to provide a conductive coating for an anode active material which prevents passivation at the surface of the anode adjacent the electrolyte.
- FIG. 1 is an illustration of a cross- section of a lithium battery or cell embodying the invention.
- an electrochemical cell or battery 10 has a negative electrode side 12, a positive electrode side 14, and a electrolyte separator 16 therebetween.
- a battery may consist of one cell or multiple cells.
- the negative electrode side 12 is the anode during discharge, and the positive electrode side 14 is the cathode during discharge.
- the negative electrode side 12 includes current collector 18, typically of nickel, iron, aluminum, stainless steel, and/or copper foil, and a body of negative electrode active material 20.
- the negative electrode active material 20 preferably consists of metallic lithium or compounds or alloys thereof, and is sometimes simply referred to as the negative electrode.
- the body of the negative electrode 20 has first and second opposed major surfaces 30, 32.
- the first surface 30 faces electrolyte separator 16 and the second surface 32 faces current collector 18.
- the positive electrode side 14 includes current collector 22, typically of aluminum, nickel, iron, stainless steel, and/or copper, and a body of positive electrode active material 24.
- the positive electrode active material 24 is sometimes simply referred to as the positive electrode.
- the positive electrode active material is preferably transition metal chalcogen compound having a reversible lithium insertion ability, wherein the transition metal is at least one selected from the group consisting of Ti, V, Cr, Mn, Fe, Nb, Mo, Ta and , and the chalcogen is at least one selected from the group consisting of 0, S and Se.
- the body of the positive electrode 24 has first and second opposed major surfaces 40,42. The first surface 40 faces the electrolyte separator 16 and the second surface 42 faces current collector 22.
- the separator 16 is typically a solid electrolyte, electrolyte separator.
- a suitable electrolyte separator is described in U.S. Patent No. 4,830,939 incorporated herein by reference.
- the electrolyte separator is a solid, preferably polymeric matrix, containing an ionically conductive liquid with an alkali metal salt where the liquid is an aprotic polar solvent.
- solid electrolyte and “electrolyte separator” are used interchangeably in industry.
- the term “separator” is used.
- the rechargeability of lithium batteries is limited by the cyclability of the lithium metal anode which converts to high surface area powder during cycling. This is called “passivation" and it occurs at the surface 30 facing the electrolyte separator 16.
- the lithium powder is highly reactive and may ignite if the battery is heated as by short circuit, other high current drain or external heat source, or if punctured causing reaction between lithium and the ambient atmosphere.
- a conductive layer of polymeric material and iodine 36 is disposed between the first surface 30 of negative electrode 20 and electrolyte separator 16.
- the coating 36 is carried on the first surface 30 of the negative electrode 20.
- the layer comprises a polymer which is polyvinyl pyridine or a derivative thereof and iodine in ionic or particle form dispersed with and complexed with the polymer.
- the term “complex” refers to any single phase iodine and polyvinyl pyridine (PVP) mixture.
- PVP polyvinyl pyridine
- Polyvinyl pyridine, and its derivatives including poly-2-vinylpyridine and poly-2- vinylquinoline (poly-2-vinyl-benzo[b] pyridine) are generally referred to as PVP.
- Poly-2-vinylpyridine may be abbreviated as P2VP
- poly-2-vinylquinoline may be abbreviated as P2VQ.
- I 2 /PVP refers to a material composed of a "complex” and also includes excess iodine and/or PVP present as a solid phase, the overall amount of initial iodine contained in the material being expressed in terms of weight percent, as is the overall amount of the poly-2-vinylpyridine. It is required that sufficient iodine be present to render the PVP layer conductive. Thus, the theoretical lower limit is greater than zero iodine, since PVP alone is not very conductive. It is thought that too much iodine is undesirable because too much I 2 results in a hard material which will have a tendency to break or crack whereby electrolyte components. can leak through the layer and react with lithium.
- A. basic pyridine unit contains one nitrogen atom.
- the basic pyridine unit has the general formula C 5 H 5 N. It is desirable to have at least 2 moles of I 2 for each basic pyridine unit. This is also conveniently expressed as at least 2 moles of I 2 for each atom of nitrogen in the basic pyridine unit.
- This relative amount of I 2 to PVP polymer pertains to any pyridine derivative. It is desirable to have up to about 15 moles of I 2 for each atom of nitrogen in the pyridine unit. As much as 24 parts I 2 to one part polymer unit or nitrogen thereof has been known to remain flexible.
- the layer 36 of I 2 /PVP complex prevents passivation and resolves safety and cyclability problems associated with lithium electrodes by preventing contact between the electrolyte and the metallic lithium. This prevents degradation caused by reaction between these two components of the cell.
- the layer 36 which separates the lithium and the electrolyte is both lithium ion conductive and electronic conductive.
- the characteristics of the preferred P 2 VP-I 2 mixtures have been reported by others, where such mixtures are used as a positive electrode (cathode) active material. Such cathode materials are reported in the literature and patents. The following describes physical properties of PVP, P2VP, and I 2 /PVP and they are incorporated herein by reference in their entirety: U.S. Patent Nos.
- a typical composition which gives a plastic flexible coating, comprises 2 to 15 moles of I 2 for each atom of N (in PVP, preferably poly-2-vinylpyridine) , as stated in RE31,532 (reissue of U.S. Patent No. 3,674,562).
- PVP poly-2-vinylpyridine
- the composition is 7 to 24 parts of I 2 to 1 part of polymer, and the average molecular weight of the polymer is typically 13,000.
- the PVP may be substituted with other polymers such as poly-2- vinylquinoline described in U.S. Patent No.
- pyridine-containing polymers are used in lithium/iodine batteries as a positive electrode (cathode) .
- cathode positive electrode
- I 2 /PVP protective coating on an anode is not known to have been suggested.
- I 2 /PVP layer Methods for forming an I 2 /PVP layer are as described in the following patents incorporated herein by reference in their entirety: 4,340,651 (Howard); RE31,532 (Schneider reissue of 3,674,562); 4,182,798; 3,773,557; 3,957,533 and 4,071,662 (Mead).
- Howard et al describes forming a cathode material of the iodine poly-2-vinylpyridine type containing various amounts of iodine.
- the conventional preparation of iodine poly-2-vinylpyridine cathode material involves heating the constituents at various temperatures and times.
- the temperatures range from about 93°C (200°F) to 150°C (300°F) and the time of heating may range from hours to days.
- the heat reaction in this instance is in the order of about 200°F to 300°F, preferably 250°F.
- the cathode material is heated to a temperature greater than the crystallization temperature of iodine.
- the materials may be prepared from mixtures of iodine and poly-2-vinylpyridine by mixing the. components together and holding them at 300°F.
- the ratio described for iodine to poly-2-vinylpyridine by weight varies up to about 95.2% by weight iodine.
- Poly-2-vinylpyridine is commercially available from various chemical companies, and at a wide-range of molecular weights. If desired, the polymer may also be synthesized as follows: Benzoyl peroxide (2.0 grams) is dissolved in freshly distilled 2-vinylpyridine (200 grams) . Water (400 ml) is added and the mixture is purged with nitrogen for 1 hour. With continued purging, the mixture is heated at 85°C (184.5°F) with stirring and kept at that temperature for 2 hours. The organic phase thickens and develops a brown color during this time.
- the mixture is cooled; the aqueous phase is discarded and the organic phase is dried overnight at 60°C (140°F) in a vacuum oven.
- the residue is ground into fine granules and dried to a constant weight at 60°C (140°F) in a vacuum oven.
- the yield is about 162 grams (81%) poly-2-vinylpyridine.
- the average molecular weight of the polymer product is preferably greater than 13,000. Theoretically, there is no upper limit and molecular weights over 100,000 are known. It can be seen from the above discussion that iodine poly-2-vinylpyridine materials may be prepared in various physical forms and utilizing differing molecular weight polymer.
- the preferred I 2 /P2PV material may be prepared by heating the poly-2-vinylpyridine and iodine mixture, or the ⁇ oly-2-vinylpyridine can be heated with lesser amounts of iodine followed by subsequent addition of appropriate amounts of iodine, in the conventional manner i.e. to a temperature greater than the crystallization temperature of iodine, but below about 150°C (300°F) . For example, heating to 200°F to 300°F is satisfactory and it may be maintained for several hours or days.
- the resulting mixture while at temperature is a flowable substance which may be shaped into a thin sheet or applied as a coating since it substantially solidifies into a relatively solid material upon cooling.
- the I 2 /P2VP mixture is at or near ordinary ambient room temperatures a putty-like, pliable solid that is sufficiently plastic to be spread on or applied to a solid substrate, such as a sheet of anode metal.
- the materials are useable in cells at temperatures up to the point where softening causes loss of dimensional stability. This point depends on the degree of polymerization of the organic component of the I 2 /P2VP charge transfer complex. It is believed that the plastic state of the materials permits excellent atomic bonding of the materials to the anode.
- the coating protects the anode from reaction with the lithium because the I 2 reacts with lithium to form Lil which, contrary to the I 2 and the polymers, is an ionic conductor of lithium ions and we want, therefore, all I 2 to be converted to Lil.
- the conductivity of this electrolyte is not very high, typically 10' 7 S/cm at 25°C for pure and probably not much higher for the mixture. Assuming the conductivity to be 10 '7 S/cm and a current density of 1 mA/cm 2 in the battery, the associated resistances and voltage drops as function of the layer thickness of the coating are given in the table. A voltage drop of the order of 100 mV about may be acceptable, which means that the upper limit of the thickness of the coating is on the order of 0.0001 ⁇ m and maximum 0.001 ⁇ m.
- metal ions such as lithium (Li+) are transported through the iodine-polymer layer disposed between the negative electrode and the electrolyte. By this mechanism, direct interaction between metallic lithium and electrolyte is avoided. Accordingly, passivation at the surface of the negative electrode is prevented or at least reduced.
- the iodine reacts with lithium to form Lil at the anode.
- the I 2 /PVP coating on the lithium anode prevents reaction between the lithium anode and organic electrolyte components and the electrolyte salt.
- the thickness of the I 2 /PVP layer should be on the order of micron size. The thickness should be less than 100 microns, and preferably less than 10 microns.
Abstract
In a preferred battery, a negative electrode contains metallic lithium, a positive electrode contains transition metal chalcogen compound having a reversible lithium insertion ability, a solid electrolyte is disposed between the electrodes, and a protective layer is disposed between the solid electrolyte and the negative electrode. The protective layer contains polyvinyl pyridine (PVP) or derivatives thereof and iodine complexed with the PVP or derivatives thereof for reducing passivation of the lithium-containing negative electrode. Preferably the polyvinyl pyridine is poly-2-vinylpyridine or poly-2-vinylquinoline.
Description
LAYER FOR STABILIZATION OF LITHIUM ANODE
Field of the Invention
This invention relates to electrochemical batteries, and more particularly, to improved electrode and electrode-current collector assemblies for such batteries.
Background of the Invention
Batteries, with metallic electrodes, have a limited life-cycle due to the degradation of the metallic electrodes. For example, lithium, when used as the negative electrode, is attacked and/or passivated by electrolytes. This results in formation of lithium powder with a very high surface area at the interface between the metallic lithium and the electrolyte. The formation of high surface area lithium powder is undesirable because it reacts violently with moisture and air and results in degradation of cell performance.
Composite anode alternatives have been suggested to overcome such problems, but they are prone to a large loss of capacity as compared to metallic lithium. Lithium alloy active materials have a relatively short cycle life due to mechanical degradation of the electrode.
Therefore, what is needed is a cell construction and method of operation which overcomes problems with passivation in order to prevent degradation of cell performance.
Summary of the Invention
According to one aspect of the invention, there is provided an electrochemical cell which has a negative electrode which comprises a solid body comprising an active metal material preferably consisting of lithium metal or compounds thereof and having a major surface facing an electrolyte or an electrolyte separator; and a layer disposed between the major surface of the negative electrode and the electrolyte. Preferably, the layer is a coating carried on the major surface of the negative electrode. The coating comprises an organic polymer material intermingled with iodine forming a polymer- iodine complex. Desirably, the iodine is in ionic or particle form and dispersed with the polymer. The coating is a conductor of electrons and a conductor of the active metal ions (Li+) of the negative electrode. The coating is of a thickness sufficient to restrict penetration of electrolyte therethrough, while at the same time, conduct electrons and positive lithium ions. Desirably, the organic polymer is polyvinyl pyridine
(PVP) or derivatives thereof such as poly-2-vinylpyridine (P2VP) , and the polymer is impregnated with particles of iodine.
The anode coating of the invention is useful for protecting metallic lithium anodes in batteries having cathodes which do not include iodine as an active material. Preferred cathode active materials include transition metal chalcogen compound having a reversible lithium insertion ability, wherein the transition metal is at least one selected from the group consisting of Ti, V, Cr, Mn, Fe, Nb, Mo, Ta and , and the chalcogen is at least one selected from the group consisting of 0, S and Se.
Accordingly, it is an object of the present invention to provide an improved electrochemical battery based on lithium which maintains its integrity over a prolonged life-cycle as compared to presently used batteries. Another object is to provide a conductive coating for an anode active material which prevents passivation at the surface of the anode adjacent the electrolyte.
These and other objects, features and advantages will become apparent from the following description of the preferred embodiments, appended claims and accompanying drawings.
Brief Description of the Drawing The figure is an illustration of a cross- section of a lithium battery or cell embodying the invention.
Detailed Description of the Preferred Embodiments As shown in the figure, an electrochemical cell or battery 10 has a negative electrode side 12, a positive electrode side 14, and a electrolyte separator 16 therebetween. In accordance with common usage, a battery may consist of one cell or multiple cells. The negative electrode side 12 is the anode during discharge, and the positive electrode side 14 is the cathode during discharge. The negative electrode side 12 includes current collector 18, typically of nickel, iron, aluminum, stainless steel, and/or copper foil, and a body of negative electrode active material 20. The negative electrode active material 20, preferably consists of metallic lithium or compounds or alloys thereof, and is sometimes simply referred to as the negative electrode.
The body of the negative electrode 20 has first and second opposed major surfaces 30, 32. The first surface 30 faces electrolyte separator 16 and the second surface 32 faces current collector 18. The positive electrode side 14 includes current collector 22, typically of aluminum, nickel, iron, stainless steel, and/or copper, and a body of positive electrode active material 24. The positive electrode active material 24 is sometimes simply referred to as the positive electrode. The positive electrode active material is preferably transition metal chalcogen compound having a reversible lithium insertion ability, wherein the transition metal is at least one selected from the group consisting of Ti, V, Cr, Mn, Fe, Nb, Mo, Ta and , and the chalcogen is at least one selected from the group consisting of 0, S and Se. The body of the positive electrode 24 has first and second opposed major surfaces 40,42. The first surface 40 faces the electrolyte separator 16 and the second surface 42 faces current collector 22.
The separator 16 is typically a solid electrolyte, electrolyte separator. A suitable electrolyte separator is described in U.S. Patent No. 4,830,939 incorporated herein by reference. The electrolyte separator is a solid, preferably polymeric matrix, containing an ionically conductive liquid with an alkali metal salt where the liquid is an aprotic polar solvent. The terms "solid electrolyte" and "electrolyte separator" are used interchangeably in industry. Sometimes, the term "separator" is used.
The rechargeability of lithium batteries is limited by the cyclability of the lithium metal anode which converts to high surface area powder during cycling. This is called "passivation" and it occurs at the surface 30 facing the electrolyte separator 16.
Electronic contact to the powder is lost and the capacity of the battery decreases. Furthermore, the lithium powder is highly reactive and may ignite if the battery is heated as by short circuit, other high current drain or external heat source, or if punctured causing reaction between lithium and the ambient atmosphere.
According to one aspect of the invention, to prevent passivation a conductive layer of polymeric material and iodine 36 is disposed between the first surface 30 of negative electrode 20 and electrolyte separator 16. Preferably, the coating 36 is carried on the first surface 30 of the negative electrode 20. Preferably, the layer comprises a polymer which is polyvinyl pyridine or a derivative thereof and iodine in ionic or particle form dispersed with and complexed with the polymer.
For descriptive purposes herein, the term "complex" refers to any single phase iodine and polyvinyl pyridine (PVP) mixture. Polyvinyl pyridine, and its derivatives including poly-2-vinylpyridine and poly-2- vinylquinoline (poly-2-vinyl-benzo[b] pyridine) are generally referred to as PVP. Poly-2-vinylpyridine may be abbreviated as P2VP, and poly-2-vinylquinoline may be abbreviated as P2VQ. The term "I2/PVP" refers to a material composed of a "complex" and also includes excess iodine and/or PVP present as a solid phase, the overall amount of initial iodine contained in the material being expressed in terms of weight percent, as is the overall amount of the poly-2-vinylpyridine.
It is required that sufficient iodine be present to render the PVP layer conductive. Thus, the theoretical lower limit is greater than zero iodine, since PVP alone is not very conductive. It is thought that too much iodine is undesirable because too much I2 results in a hard material which will have a tendency to break or crack whereby electrolyte components. can leak through the layer and react with lithium. It should be noted that too high an amount of polymer may result in either an insulating film or a liquid interface layer. A. basic pyridine unit contains one nitrogen atom. The basic pyridine unit has the general formula C5H5N. It is desirable to have at least 2 moles of I2 for each basic pyridine unit. This is also conveniently expressed as at least 2 moles of I2 for each atom of nitrogen in the basic pyridine unit. This relative amount of I2 to PVP polymer pertains to any pyridine derivative. It is desirable to have up to about 15 moles of I2 for each atom of nitrogen in the pyridine unit. As much as 24 parts I2 to one part polymer unit or nitrogen thereof has been known to remain flexible. The layer 36 of I2/PVP complex prevents passivation and resolves safety and cyclability problems associated with lithium electrodes by preventing contact between the electrolyte and the metallic lithium. This prevents degradation caused by reaction between these two components of the cell. The layer 36 which separates the lithium and the electrolyte is both lithium ion conductive and electronic conductive. The characteristics of the preferred P2VP-I2 mixtures have been reported by others, where such mixtures are used as a positive electrode (cathode) active material. Such cathode materials are reported in the literature and patents. The following describes physical properties of PVP, P2VP, and I2/PVP and they are
incorporated herein by reference in their entirety: U.S. Patent Nos. 4,340,651 (Howard); RE31,532 and 4,148,975 (Schneider); 4,182,798 (Skarstad) and 3,773,557. A typical composition, which gives a plastic flexible coating, comprises 2 to 15 moles of I2 for each atom of N (in PVP, preferably poly-2-vinylpyridine) , as stated in RE31,532 (reissue of U.S. Patent No. 3,674,562). In another example, the composition is 7 to 24 parts of I2 to 1 part of polymer, and the average molecular weight of the polymer is typically 13,000. The PVP may be substituted with other polymers such as poly-2- vinylquinoline described in U.S. Patent No. 4,148,975 incorporated herein by reference in its entirety. Some pyridine-containing polymers are used in lithium/iodine batteries as a positive electrode (cathode) . (See A.A. Schneider et al, "Performance Characteristics of a Long Life Pacemaker Cell", in D.H. Collins (ed.), Power Sources 5, Proc. 9th Int. Symp. , Brighton 1974, Academic Press, London 1975.) However, I2/PVP protective coating on an anode is not known to have been suggested. Methods for forming an I2/PVP layer are as described in the following patents incorporated herein by reference in their entirety: 4,340,651 (Howard); RE31,532 (Schneider reissue of 3,674,562); 4,182,798; 3,773,557; 3,957,533 and 4,071,662 (Mead). Howard et al describes forming a cathode material of the iodine poly-2-vinylpyridine type containing various amounts of iodine. The conventional preparation of iodine poly-2-vinylpyridine cathode material involves heating the constituents at various temperatures and times. Generally speaking, the temperatures range from about 93°C (200°F) to 150°C (300°F) and the time of heating may range from hours to days. The heat reaction in this instance is in the order
of about 200°F to 300°F, preferably 250°F. Similarly, the cathode material is heated to a temperature greater than the crystallization temperature of iodine. Such basic methods are more fully described in Mead U.S. Patent No. 3,773,557, cited above.
The materials may be prepared from mixtures of iodine and poly-2-vinylpyridine by mixing the. components together and holding them at 300°F. The ratio described for iodine to poly-2-vinylpyridine by weight varies up to about 95.2% by weight iodine.
Poly-2-vinylpyridine is commercially available from various chemical companies, and at a wide-range of molecular weights. If desired, the polymer may also be synthesized as follows: Benzoyl peroxide (2.0 grams) is dissolved in freshly distilled 2-vinylpyridine (200 grams) . Water (400 ml) is added and the mixture is purged with nitrogen for 1 hour. With continued purging, the mixture is heated at 85°C (184.5°F) with stirring and kept at that temperature for 2 hours. The organic phase thickens and develops a brown color during this time.
The mixture is cooled; the aqueous phase is discarded and the organic phase is dried overnight at 60°C (140°F) in a vacuum oven. The residue is ground into fine granules and dried to a constant weight at 60°C (140°F) in a vacuum oven. The yield is about 162 grams (81%) poly-2-vinylpyridine. The average molecular weight of the polymer product is preferably greater than 13,000. Theoretically, there is no upper limit and molecular weights over 100,000 are known. It can be seen from the above discussion that iodine poly-2-vinylpyridine materials may be prepared in various physical forms and utilizing differing molecular weight polymer. Moreover, it has become generally accepted that various amounts of iodine can be included in the conventionally prepared material.
In order to form an I2/PVP protective coating or layer for an anode, the preferred I2/P2PV material, may be prepared by heating the poly-2-vinylpyridine and iodine mixture, or the ρoly-2-vinylpyridine can be heated with lesser amounts of iodine followed by subsequent addition of appropriate amounts of iodine, in the conventional manner i.e. to a temperature greater than the crystallization temperature of iodine, but below about 150°C (300°F) . For example, heating to 200°F to 300°F is satisfactory and it may be maintained for several hours or days. Various combinations of times and temperatures within these ranges may be used as previously described hereinabove. The resulting mixture while at temperature is a flowable substance which may be shaped into a thin sheet or applied as a coating since it substantially solidifies into a relatively solid material upon cooling.
Further, the I2/P2VP mixture is at or near ordinary ambient room temperatures a putty-like, pliable solid that is sufficiently plastic to be spread on or applied to a solid substrate, such as a sheet of anode metal. The materials are useable in cells at temperatures up to the point where softening causes loss of dimensional stability. This point depends on the degree of polymerization of the organic component of the I2/P2VP charge transfer complex. It is believed that the plastic state of the materials permits excellent atomic bonding of the materials to the anode.
The coating protects the anode from reaction with the lithium because the I2 reacts with lithium to form Lil which, contrary to the I2 and the polymers, is an ionic conductor of lithium ions and we want, therefore, all I2 to be converted to Lil.
Table 1
Layer Thickness Resistance Voltage Drop
(um ) (ohm) (V)
1 1.000.000 1000
0.1 1.00.000 100
0.01 10.000 10
0.001 1.000 1
0.0001 100 0.1
0.00001 10 0.01
0.000001 1 0.001
However, the conductivity of this electrolyte is not very high, typically 10'7 S/cm at 25°C for pure and probably not much higher for the mixture. Assuming the conductivity to be 10'7 S/cm and a current density of 1 mA/cm2 in the battery, the associated resistances and voltage drops as function of the layer thickness of the coating are given in the table. A voltage drop of the order of 100 mV about may be acceptable, which means that the upper limit of the thickness of the coating is on the order of 0.0001 μm and maximum 0.001 μm. In use, metal ions, such as lithium (Li+) are transported through the iodine-polymer layer disposed between the negative electrode and the electrolyte. By this mechanism, direct interaction between metallic lithium and electrolyte is avoided. Accordingly, passivation at the surface of the negative electrode is prevented or at least reduced.
Further, the iodine reacts with lithium to form Lil at the anode. Thus, the I2/PVP coating on the lithium anode prevents reaction between the lithium anode and organic electrolyte components and the electrolyte salt. Due to the relatively low conductivity of the Lil, at about 10"7
Siemens/cm (S/cm) , the thickness of the I2/PVP layer should be on the order of micron size. The thickness should be less than 100 microns, and preferably less than 10 microns. While this invention has been described in terms of certain embodiments thereof, it is not intended that it be limited to the above description, .but rather only to the extent set forth in the following claims. The embodiments of the invention in which an exclusive property or privilege is claimed are defined in the appended claims.
Claims
1. In a battery comprising a negative electrode body having an active material which comprises metallic lithium, a positive electrode body including an active material having a reversible lithium insertion ability, and an electrolyte separator comprising a solid matrix material and an electrolyte having a salt of lithium, the matrix material being disposed between the positive and negative electrode bodies, the improvement comprising a layer disposed between the matrix material and a surface of the negative electrode body facing the matrix material, said layer being electronically conductive and ionically conductive of lithium ions and comprising a polymer and iodine dispersed with said polymer, said polymer having a number of monomers, each of such monomers having a pyridine-based unit forming a charge transfer complex with said iodine for reducing passivation of said lithium-containing negative electrode.
2. The battery of claim 1, wherein said polymer contains one nitrogen atom per each pyridine unit thereof and said iodine is present in an amount equivalent to at least about 2 moles I2 for each nitrogen atom.
3. The battery of claim 1, wherein said polymer is selected from the group consisting of poly-2- vinylpyridine and poly-2-vinylquinoline.
The battery according to claim 1, wherein the polymer is poly-2-vinylpyridine.
5. In a battery comprising a negative electrode having an active material which comprises metallic lithium and an electrolyte separator comprising a solid matrix material and an electrolyte having a salt of lithium, the negative electrode having a major surface facing the matrix material, the improvement *comprising a layer disposed between the solid matrix material and the major surface of the negative electrode, said layer being electronically conductive and ionically conductive of lithium ions and comprising a polymer and iodine dispersed with said polymer,said polymer having a number of monomers, each of such monomers having a pyridine- based unit forming a charge transfer complex with said iodine for reducing passivation of said lithium- containing negative electrode.
6. The battery of claim 5, wherein said polymer contains one nitrogen atom per each pyridine unit thereof and said iodine is present in an amount equivalent to at least about 2 moles I2 for each nitrogen atom.
7. The battery of claim 5, wherein said polymer is selected from the group consisting of poly-2- vinylpyridine and poly-2-vinylquinoline.
8. The battery according to claims 5, wherein the polymer is poly-2-vinylpyridine.
9. A battery comprising: a) a negative electrode having an active material which comprises metallic lithium; b) a positive electrode including an active material having a reversible lithium insertion ability; c) an electrolyte separator comprising a polymeric matrix material and an electrolyte having a salt of lithium, the solid matrix material being disposed between the positive and negative electrodes; and d) a layer disposed between the solid matrix material and the surface of the negative electrode facing the matrix material, said layer being electronically conductive and ionically conductive of lithium ions and comprising a polymer and iodine dispersed with said polymer, said polymer having a number of monomers, each of such monomers having a pyridine- based unit forming a charge transfer complex with said iodine for reducing passivation of said lithium-containing negative electrode.
10. The battery according to claim 9, wherein the active material comprises a transition metal chalcogen compound, transition metal is at least one selected from the group consisting of Ti, V, Cr, Mn, Fe, Nb, Mo, Ta and W, and the chalcogen is at least one selected from the group consisting of O, S, and Se.
11.
The battery according to claim 9, wherein said transition metal chalcogen optionally includes lithium.
12. The battery according to claim 9, wherein the polymer is poly-2-vinylpyridine.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU64125/94A AU6412594A (en) | 1993-03-30 | 1994-03-17 | Layer for stabilization of lithium anode |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/040,228 | 1993-03-30 | ||
US08/040,228 US5342710A (en) | 1993-03-30 | 1993-03-30 | Lakyer for stabilization of lithium anode |
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WO1994023468A1 true WO1994023468A1 (en) | 1994-10-13 |
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PCT/US1994/002976 WO1994023468A1 (en) | 1993-03-30 | 1994-03-17 | Layer for stabilization of lithium anode |
Country Status (3)
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US (2) | US5342710A (en) |
AU (1) | AU6412594A (en) |
WO (1) | WO1994023468A1 (en) |
Families Citing this family (126)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5961672A (en) * | 1994-02-16 | 1999-10-05 | Moltech Corporation | Stabilized anode for lithium-polymer batteries |
US5434021A (en) * | 1994-08-12 | 1995-07-18 | Arthur D. Little, Inc. | Secondary electrolytic cell and electrolytic process |
US5503946A (en) * | 1994-09-29 | 1996-04-02 | Arthur D. Little, Inc. | Particulate interface for electrolytic cells and electrolytic process |
JP2885654B2 (en) * | 1994-12-06 | 1999-04-26 | 科学技術振興事業団 | Method for producing nitrogen-containing carbon material |
US5604056A (en) * | 1995-05-09 | 1997-02-18 | Fauteux; Denis G. | Electrolytic cell and process for treating an alkali metal electrode |
US5654113A (en) * | 1995-06-07 | 1997-08-05 | Comsat Corporation | Protonated cathode battery |
JP4083224B2 (en) * | 1996-06-14 | 2008-04-30 | サイオン パワー コーポレイション | Composition useful for electrolyte of secondary battery cell |
WO1998037589A1 (en) * | 1997-02-21 | 1998-08-27 | Motorola Inc. | Polymeric electrolyte and electrochemical cell using same |
US6402795B1 (en) | 1998-02-18 | 2002-06-11 | Polyplus Battery Company, Inc. | Plating metal negative electrodes under protective coatings |
US6214061B1 (en) | 1998-05-01 | 2001-04-10 | Polyplus Battery Company, Inc. | Method for forming encapsulated lithium electrodes having glass protective layers |
US6495287B1 (en) | 1999-05-20 | 2002-12-17 | Mitsubishi Cehmical Corporation | Electrochemical cell having a pre-passivated electrode and associated fabrication process |
US6416901B1 (en) | 1999-07-06 | 2002-07-09 | Mitsubishi Chemical Corporation | Electrochemical cell having an interface modifying component and associated fabrication process |
US7163713B2 (en) * | 1999-07-31 | 2007-01-16 | The Regents Of The University Of California | Method for making dense crack free thin films |
US6413285B1 (en) | 1999-11-01 | 2002-07-02 | Polyplus Battery Company | Layered arrangements of lithium electrodes |
US6413284B1 (en) | 1999-11-01 | 2002-07-02 | Polyplus Battery Company | Encapsulated lithium alloy electrodes having barrier layers |
US6733924B1 (en) | 1999-11-23 | 2004-05-11 | Moltech Corporation | Lithium anodes for electrochemical cells |
US20110165471A9 (en) * | 1999-11-23 | 2011-07-07 | Sion Power Corporation | Protection of anodes for electrochemical cells |
US6797428B1 (en) * | 1999-11-23 | 2004-09-28 | Moltech Corporation | Lithium anodes for electrochemical cells |
US7247408B2 (en) | 1999-11-23 | 2007-07-24 | Sion Power Corporation | Lithium anodes for electrochemical cells |
JP5106732B2 (en) | 1999-11-23 | 2012-12-26 | シオン・パワー・コーポレーション | Lithium negative electrode for electrochemical cells |
US7771870B2 (en) * | 2006-03-22 | 2010-08-10 | Sion Power Corporation | Electrode protection in both aqueous and non-aqueous electrochemical cells, including rechargeable lithium batteries |
US6767662B2 (en) | 2000-10-10 | 2004-07-27 | The Regents Of The University Of California | Electrochemical device and process of making |
US6632573B1 (en) * | 2001-02-20 | 2003-10-14 | Polyplus Battery Company | Electrolytes with strong oxidizing additives for lithium/sulfur batteries |
CN1179432C (en) | 2001-05-31 | 2004-12-08 | 三星Sdi株式会社 | Method for forming lithium metal positive-pole protective layer of lithium cell |
KR100425585B1 (en) * | 2001-11-22 | 2004-04-06 | 한국전자통신연구원 | Lithium polymer secondary battery having crosslinked polymer protective thin film and method for manufacturing the same |
US6740441B2 (en) | 2001-12-18 | 2004-05-25 | The Regents Of The University Of California | Metal current collect protected by oxide film |
WO2003051529A1 (en) * | 2001-12-18 | 2003-06-26 | The Regents Of The University Of California | A process for making dense thin films |
US6911280B1 (en) * | 2001-12-21 | 2005-06-28 | Polyplus Battery Company | Chemical protection of a lithium surface |
US7232626B2 (en) * | 2002-04-24 | 2007-06-19 | The Regents Of The University Of California | Planar electrochemical device assembly |
US20040023101A1 (en) * | 2002-05-07 | 2004-02-05 | The Regents Of The University Of California | Electrochemical cell stack assembly |
DE10228201B4 (en) * | 2002-06-24 | 2006-12-21 | Chemetall Gmbh | Process for the preparation of lithium iodide solutions |
JP4879490B2 (en) * | 2002-10-04 | 2012-02-22 | ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア | Fluorine separator and generator |
KR100449765B1 (en) * | 2002-10-12 | 2004-09-22 | 삼성에스디아이 주식회사 | Lithium metal anode for lithium battery |
AU2003301383B2 (en) * | 2002-10-15 | 2009-12-10 | Polyplus Battery Company | Ionically conductive composites for protection of active metal anodes |
US7390591B2 (en) * | 2002-10-15 | 2008-06-24 | Polyplus Battery Company | Ionically conductive membranes for protection of active metal anodes and battery cells |
US20080057386A1 (en) * | 2002-10-15 | 2008-03-06 | Polyplus Battery Company | Ionically conductive membranes for protection of active metal anodes and battery cells |
US7645543B2 (en) * | 2002-10-15 | 2010-01-12 | Polyplus Battery Company | Active metal/aqueous electrochemical cells and systems |
US7282302B2 (en) * | 2002-10-15 | 2007-10-16 | Polyplus Battery Company | Ionically conductive composites for protection of active metal anodes |
GB0302834D0 (en) * | 2003-02-07 | 2003-03-12 | Aea Technology Battery Systems | Secondary cell with tin anode |
US7968235B2 (en) * | 2003-07-17 | 2011-06-28 | Uchicago Argonne Llc | Long life lithium batteries with stabilized electrodes |
KR100542213B1 (en) * | 2003-10-31 | 2006-01-10 | 삼성에스디아이 주식회사 | Negative electrode of lithium metal battery and lithium metal battery comprisng same |
US7491458B2 (en) | 2003-11-10 | 2009-02-17 | Polyplus Battery Company | Active metal fuel cells |
US7608178B2 (en) * | 2003-11-10 | 2009-10-27 | Polyplus Battery Company | Active metal electrolyzer |
US10629947B2 (en) * | 2008-08-05 | 2020-04-21 | Sion Power Corporation | Electrochemical cell |
US7282295B2 (en) | 2004-02-06 | 2007-10-16 | Polyplus Battery Company | Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture |
US9368775B2 (en) | 2004-02-06 | 2016-06-14 | Polyplus Battery Company | Protected lithium electrodes having porous ceramic separators, including an integrated structure of porous and dense Li ion conducting garnet solid electrolyte layers |
US9012096B2 (en) * | 2004-05-28 | 2015-04-21 | Uchicago Argonne, Llc | Long life lithium batteries with stabilized electrodes |
US20060078790A1 (en) * | 2004-10-05 | 2006-04-13 | Polyplus Battery Company | Solid electrolytes based on lithium hafnium phosphate for active metal anode protection |
US7951510B2 (en) * | 2004-11-11 | 2011-05-31 | GM Global Technology Operations LLC | Electroconductive polymer coating on electroconductive elements in a fuel cell |
JP2008532248A (en) * | 2005-03-02 | 2008-08-14 | ウチカゴ アルゴン、エルエルシー | A novel redox transfer material to prevent overcharge of lithium batteries |
WO2006101779A2 (en) * | 2005-03-15 | 2006-09-28 | The University Of Chicago | Non-aqueous electrolytes for lithium ion batteries |
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US7968231B2 (en) * | 2005-12-23 | 2011-06-28 | U Chicago Argonne, Llc | Electrode materials and lithium battery systems |
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EP2067198A2 (en) | 2006-09-25 | 2009-06-10 | Board of Regents, The University of Texas System | Cation-substituted spinel oxide and oxyfluoride cathodes for lithium ion batteries |
WO2008070059A2 (en) | 2006-12-04 | 2008-06-12 | Sion Power Corporation | Separation of electrolytes in lithium batteries |
US8021496B2 (en) | 2007-05-16 | 2011-09-20 | Fmc Corporation | Stabilized lithium metal powder for Li-ion application, composition and process |
KR101386163B1 (en) * | 2007-07-19 | 2014-04-17 | 삼성에스디아이 주식회사 | Composite anode material, and anode and lithium battery using the same |
US8475688B2 (en) * | 2007-09-20 | 2013-07-02 | Uchicago Argonne, Llc | Lithium batteries using poly(ethylene oxide)-based non-aqueous electrolytes |
JP5305678B2 (en) * | 2008-02-07 | 2013-10-02 | 株式会社東芝 | Non-aqueous electrolyte battery and battery pack |
US8277683B2 (en) * | 2008-05-30 | 2012-10-02 | Uchicago Argonne, Llc | Nano-sized structured layered positive electrode materials to enable high energy density and high rate capability lithium batteries |
MX2010013888A (en) | 2008-06-16 | 2011-05-03 | Polyplus Battery Co Inc | Aqueous lithium/air battery cells. |
US8940443B2 (en) * | 2008-08-13 | 2015-01-27 | Greatbatch Ltd. | Polyvinylpyridine additives for nonaqueous electrolytes activating lithium rechargeable electrochemical cells |
US20110076572A1 (en) * | 2009-09-25 | 2011-03-31 | Khalil Amine | Non-aqueous electrolytes for electrochemical cells |
KR101861212B1 (en) | 2010-09-09 | 2018-06-29 | 캘리포니아 인스티튜트 오브 테크놀로지 | Electrochemical Energy Storage Systems and Methods |
US9093722B2 (en) | 2010-09-30 | 2015-07-28 | Uchicago Argonne, Llc | Functionalized ionic liquid electrolytes for lithium ion batteries |
CA2724307A1 (en) * | 2010-12-01 | 2012-06-01 | Hydro-Quebec | Lithium-air battery |
EP2721665B1 (en) | 2011-06-17 | 2021-10-27 | Sion Power Corporation | Plating technique for electrode |
US9379368B2 (en) | 2011-07-11 | 2016-06-28 | California Institute Of Technology | Electrochemical systems with electronically conductive layers |
US10158110B2 (en) | 2011-07-11 | 2018-12-18 | California Institute Of Technology | Separators for electrochemical systems |
US9660311B2 (en) | 2011-08-19 | 2017-05-23 | Polyplus Battery Company | Aqueous lithium air batteries |
JP6118805B2 (en) | 2011-10-13 | 2017-04-19 | シオン・パワー・コーポレーション | Electrode structure and manufacturing method thereof |
US8828574B2 (en) | 2011-11-15 | 2014-09-09 | Polyplus Battery Company | Electrolyte compositions for aqueous electrolyte lithium sulfur batteries |
US8828573B2 (en) | 2011-11-15 | 2014-09-09 | Polyplus Battery Company | Electrode structures for aqueous electrolyte lithium sulfur batteries |
US8828575B2 (en) | 2011-11-15 | 2014-09-09 | PolyPlus Batter Company | Aqueous electrolyte lithium sulfur batteries |
US9660265B2 (en) | 2011-11-15 | 2017-05-23 | Polyplus Battery Company | Lithium sulfur batteries and electrolytes and sulfur cathodes thereof |
JP5951798B2 (en) * | 2012-01-05 | 2016-07-13 | アウディ アクチェンゲゼルシャフトAudi Ag | Method for manufacturing a plurality of fuel cell separator plate assemblies |
JP6396284B2 (en) * | 2012-04-10 | 2018-10-03 | カリフォルニア インスティチュート オブ テクノロジー | New separator for electrochemical systems |
US8932771B2 (en) | 2012-05-03 | 2015-01-13 | Polyplus Battery Company | Cathode architectures for alkali metal / oxygen batteries |
US9005311B2 (en) | 2012-11-02 | 2015-04-14 | Sion Power Corporation | Electrode active surface pretreatment |
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US10714724B2 (en) | 2013-11-18 | 2020-07-14 | California Institute Of Technology | Membranes for electrochemical cells |
US20150171398A1 (en) | 2013-11-18 | 2015-06-18 | California Institute Of Technology | Electrochemical separators with inserted conductive layers |
US11038165B2 (en) * | 2014-05-29 | 2021-06-15 | Sila Nanotechnologies, Inc. | Ion permeable composite current collectors for metal-ion batteries and cell design using the same |
US11038178B2 (en) | 2014-09-09 | 2021-06-15 | Sion Power Corporation | Protective layers in lithium-ion electrochemical cells and associated electrodes and methods |
WO2016069749A1 (en) * | 2014-10-28 | 2016-05-06 | University Of Maryland, College Park | Interfacial layers for solid-state batteries methods of making same |
JP6964003B2 (en) | 2015-05-20 | 2021-11-10 | シオン・パワー・コーポレーション | Protective layer for electrodes |
US10340528B2 (en) | 2015-12-02 | 2019-07-02 | California Institute Of Technology | Three-dimensional ion transport networks and current collectors for electrochemical cells |
US10734642B2 (en) | 2016-03-30 | 2020-08-04 | Global Graphene Group, Inc. | Elastomer-encapsulated particles of high-capacity anode active materials for lithium batteries |
KR102349772B1 (en) | 2016-05-20 | 2022-01-10 | 시온 파워 코퍼레이션 | Electrode and electrochemical cell protective layer |
CN106784636A (en) * | 2016-12-29 | 2017-05-31 | 中国电子科技集团公司第十八研究所 | Method for treating surface of metal lithium by using iodine solution and application of method in solid-state battery |
US11495792B2 (en) | 2017-02-16 | 2022-11-08 | Global Graphene Group, Inc. | Method of manufacturing a lithium secondary battery having a protected high-capacity anode active material |
US10985373B2 (en) | 2017-02-27 | 2021-04-20 | Global Graphene Group, Inc. | Lithium battery cathode and method of manufacturing |
US11742475B2 (en) | 2017-04-03 | 2023-08-29 | Global Graphene Group, Inc. | Encapsulated anode active material particles, lithium secondary batteries containing same, and method of manufacturing |
US10483533B2 (en) | 2017-04-10 | 2019-11-19 | Global Graphene Group, Inc. | Encapsulated cathode active material particles, lithium secondary batteries containing same, and method of manufacturing |
US10770721B2 (en) * | 2017-04-10 | 2020-09-08 | Global Graphene Group, Inc. | Lithium metal secondary battery containing anode-protecting polymer layer and manufacturing method |
US10862129B2 (en) | 2017-04-12 | 2020-12-08 | Global Graphene Group, Inc. | Lithium anode-protecting polymer layer for a lithium metal secondary battery and manufacturing method |
US10964951B2 (en) | 2017-08-14 | 2021-03-30 | Global Graphene Group, Inc. | Anode-protecting layer for a lithium metal secondary battery and manufacturing method |
JP2021514101A (en) | 2018-02-15 | 2021-06-03 | ユニバシティ オブ メリーランド カレッジ パーク | Regular porous solid electrolyte structure, electrochemical device containing it, its manufacturing method |
US11721832B2 (en) | 2018-02-23 | 2023-08-08 | Global Graphene Group, Inc. | Elastomer composite-encapsulated particles of anode active materials for lithium batteries |
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US11005094B2 (en) | 2018-03-07 | 2021-05-11 | Global Graphene Group, Inc. | Electrochemically stable elastomer-encapsulated particles of anode active materials for lithium batteries |
US10818926B2 (en) | 2018-03-07 | 2020-10-27 | Global Graphene Group, Inc. | Method of producing electrochemically stable elastomer-encapsulated particles of anode active materials for lithium batteries |
US11043694B2 (en) | 2018-04-16 | 2021-06-22 | Global Graphene Group, Inc. | Alkali metal-selenium secondary battery containing a cathode of encapsulated selenium particles |
US10978698B2 (en) | 2018-06-15 | 2021-04-13 | Global Graphene Group, Inc. | Method of protecting sulfur cathode materials for alkali metal-sulfur secondary battery |
US11121398B2 (en) | 2018-06-15 | 2021-09-14 | Global Graphene Group, Inc. | Alkali metal-sulfur secondary battery containing cathode material particulates |
US10854927B2 (en) | 2018-06-18 | 2020-12-01 | Global Graphene Group, Inc. | Method of improving cycle-life of alkali metal-sulfur secondary battery |
US10957912B2 (en) | 2018-06-18 | 2021-03-23 | Global Graphene Group, Inc. | Method of extending cycle-life of a lithium-sulfur battery |
US10862157B2 (en) | 2018-06-18 | 2020-12-08 | Global Graphene Group, Inc. | Alkali metal-sulfur secondary battery containing a conductive electrode-protecting layer |
US10978744B2 (en) | 2018-06-18 | 2021-04-13 | Global Graphene Group, Inc. | Method of protecting anode of a lithium-sulfur battery |
US10777810B2 (en) | 2018-06-21 | 2020-09-15 | Global Graphene Group, Inc. | Lithium metal secondary battery containing a protected lithium anode |
US11276852B2 (en) | 2018-06-21 | 2022-03-15 | Global Graphene Group, Inc. | Lithium metal secondary battery containing an elastic anode-protecting layer |
US10873088B2 (en) | 2018-06-25 | 2020-12-22 | Global Graphene Group, Inc. | Lithium-selenium battery containing an electrode-protecting layer and method of improving cycle-life |
EP3591743A1 (en) | 2018-07-04 | 2020-01-08 | Kemijski Institut | Silylated cellulose interfacial protective layer on a metal surface |
US11239460B2 (en) | 2018-08-22 | 2022-02-01 | Global Graphene Group, Inc. | Method of producing electrochemically stable elastomer-encapsulated particles of cathode active materials for lithium batteries |
US11043662B2 (en) | 2018-08-22 | 2021-06-22 | Global Graphene Group, Inc. | Electrochemically stable elastomer-encapsulated particles of cathode active materials for lithium batteries |
US10886528B2 (en) | 2018-08-24 | 2021-01-05 | Global Graphene Group, Inc. | Protected particles of cathode active materials for lithium batteries |
US11223049B2 (en) | 2018-08-24 | 2022-01-11 | Global Graphene Group, Inc. | Method of producing protected particles of cathode active materials for lithium batteries |
US10971724B2 (en) | 2018-10-15 | 2021-04-06 | Global Graphene Group, Inc. | Method of producing electrochemically stable anode particulates for lithium secondary batteries |
US10971725B2 (en) | 2019-01-24 | 2021-04-06 | Global Graphene Group, Inc. | Lithium metal secondary battery containing elastic polymer foam as an anode-protecting layer |
US11791450B2 (en) | 2019-01-24 | 2023-10-17 | Global Graphene Group, Inc. | Method of improving cycle life of a rechargeable lithium metal battery |
US11569527B2 (en) | 2019-03-26 | 2023-01-31 | University Of Maryland, College Park | Lithium battery |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2420214A1 (en) * | 1978-03-13 | 1979-10-12 | Medtronic Inc | ELECTROCHEMICAL BATTERY CONTAINING A PREFORMED POLYMER SHEET ASSOCIATED WITH THE ANODE |
USRE31532E (en) * | 1970-06-01 | 1984-03-06 | Catalyst Research Corporation | Primary cells and iodine containing cathodes therefor |
EP0312330A2 (en) * | 1987-10-15 | 1989-04-19 | Wilson Greatbatch Ltd. | Anode coating for lithium cell |
EP0318161A1 (en) * | 1987-10-30 | 1989-05-31 | Mhb Joint Venture | Methods of making interpenetrating polymeric networks, anode and cathode half elements and their use in forming electrochemical cells |
EP0396324A2 (en) * | 1989-04-26 | 1990-11-07 | Mhb Joint Venture | Cells |
WO1992010860A1 (en) * | 1990-12-13 | 1992-06-25 | Medtronic, Inc. | Lithium-iodine electrochemical cells with improved end of life characteristics |
EP0528557A1 (en) * | 1991-07-29 | 1993-02-24 | Valence Technology, Inc. | Carbon/polymer composite electrode for use in a lithium battery |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3773557A (en) * | 1972-03-01 | 1973-11-20 | Wurlitzer Co | Solid state battery |
US3957533A (en) * | 1974-11-19 | 1976-05-18 | Wilson Greatbatch Ltd. | Lithium-iodine battery having coated anode |
US4148975A (en) * | 1978-04-03 | 1979-04-10 | Catalyst Research Corporation | Lithium iodine primary cells having novel pelletized depolarizer |
US4340651A (en) * | 1980-11-12 | 1982-07-20 | Medtronic, Inc. | Cathode material and high capacity lithium-iodine cells |
US4830939B1 (en) * | 1987-10-30 | 1996-10-08 | Mhb Joint Venture | Radiation cured solid electrolytes and electrochemical devices employing the same |
-
1993
- 1993-03-30 US US08/040,228 patent/US5342710A/en not_active Expired - Fee Related
-
1994
- 1994-03-17 AU AU64125/94A patent/AU6412594A/en not_active Abandoned
- 1994-03-17 WO PCT/US1994/002976 patent/WO1994023468A1/en active Application Filing
- 1994-07-06 US US08/271,302 patent/US5487959A/en not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE31532E (en) * | 1970-06-01 | 1984-03-06 | Catalyst Research Corporation | Primary cells and iodine containing cathodes therefor |
FR2420214A1 (en) * | 1978-03-13 | 1979-10-12 | Medtronic Inc | ELECTROCHEMICAL BATTERY CONTAINING A PREFORMED POLYMER SHEET ASSOCIATED WITH THE ANODE |
EP0312330A2 (en) * | 1987-10-15 | 1989-04-19 | Wilson Greatbatch Ltd. | Anode coating for lithium cell |
EP0318161A1 (en) * | 1987-10-30 | 1989-05-31 | Mhb Joint Venture | Methods of making interpenetrating polymeric networks, anode and cathode half elements and their use in forming electrochemical cells |
EP0396324A2 (en) * | 1989-04-26 | 1990-11-07 | Mhb Joint Venture | Cells |
WO1992010860A1 (en) * | 1990-12-13 | 1992-06-25 | Medtronic, Inc. | Lithium-iodine electrochemical cells with improved end of life characteristics |
EP0528557A1 (en) * | 1991-07-29 | 1993-02-24 | Valence Technology, Inc. | Carbon/polymer composite electrode for use in a lithium battery |
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---|---|
US5342710A (en) | 1994-08-30 |
AU6412594A (en) | 1994-10-24 |
US5487959A (en) | 1996-01-30 |
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