CN107749489B - High-safety high-energy-density lithium ion battery - Google Patents
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
The invention relates to a high-safety high-energy-density lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode and the negative electrode are separated by the diaphragm, a battery core is formed by winding or laminating, the battery core is packaged into a battery shell, the electrolyte is injected into the battery shell and sealed to obtain the battery, and the surface of the positive electrode or/and the negative electrode is coated with stabilized lithium metal powder with a positive temperature coefficient effect. The improvement is carried out in the battery, the internal temperature change can be sensed in time, and the first effect of the battery can be improved because a layer of stabilized lithium metal powder is coated on the surface of a battery pole piece, so that the energy density of the battery is not influenced, and the energy density of the battery can be improved; the stabilized lithium metal powder is adopted, the use is not limited by the environment, the operation is simpler, and the battery has a special positive temperature coefficient effect and can improve the safety of the battery.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a high-safety high-energy-density lithium ion battery which can improve the energy density of the battery and the safety of the battery.
Background
Lithium ion batteries have the advantages of no pollution, high energy density and power density, high voltage, long cycle life, small self-discharge, no memory effect and the like, are widely used for digital products such as mobile phones, cameras, notebook computers and the like, and are also widely used as power batteries for vehicles along with the development of electric vehicles. With the progress of science and technology, people urgently need a lithium ion battery with high energy density to meet the development trend of miniaturization and lightness and thinness of various electric appliances and the endurance mileage of electric automobiles to be promoted urgently. Therefore, most of battery manufacturers want to improve the energy density of the battery by all methods, but since the lithium ion battery forms a layer of surface passivation film (SEI film) in the initial charging and discharging process and consumes a part of lithium ions, the initial efficiency of the battery is reduced, the initial efficiency of the existing commercial lithium ion battery is about 80%, and if the initial efficiency of the battery can be improved, the energy density of the battery is also greatly improved. Researchers have proposed many proposals for improving the first efficiency of batteries, and most of them supplement lithium to the positive electrode or negative electrode of a battery with lithium metal. Such as the scheme of patent numbers CN 102916164A, CN102315422A, and the like. The lithium supplement schemes proposed in patent nos. CN 102916164a and CN102315422A use lithium metal, which is very active, and therefore the schemes are affected by the environment in use and the operation process is complicated. And the scheme does not improve the safety of the lithium ion battery.
Meanwhile, the higher the energy density of the lithium ion battery, the more unsafe the lithium ion battery becomes, and some internal side reactions are easily caused under the abuse condition or under the condition of external or internal short circuit, so that thermal runaway is caused, and danger is caused. In response to these risks, researchers have also proposed protective solutions such as external PTC elements, internal flame retardant electrolytes, ceramic coated separators, and the like.
According to the scheme provided for improving the safety of the lithium ion battery, the external PTC element cannot sense the temperature change inside the lithium ion battery in time, and the control on thermal runaway is weak. Improvements in lithium ion batteries, such as flame retardant electrolytes, ceramic coated separators, and PTC coated active material materials, all sacrifice some of the battery's electrochemical performance and energy density.
Disclosure of Invention
The invention aims to solve the defect that the thermal runaway of a lithium ion battery is weakly controlled in the prior art, and provides a high-safety high-energy-density lithium ion battery which can improve the energy density of the battery and the safety of the battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-safety high-energy-density lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode and the negative electrode are separated by the diaphragm and wound or laminated to form a battery cell, the battery cell is packaged into a battery shell, the electrolyte is injected into the battery shell and sealed to obtain the battery, and the surfaces of the positive electrode and/or the negative electrode are coated with stabilized lithium metal powder with a positive temperature coefficient effect. In the technical scheme, the interior of the battery is improved, the internal temperature change can be sensed in time, and the surface of a battery pole piece is coated with a layer of stable lithium metal powder which is conductive, so that the electrochemical performance of the battery is not influenced; the stabilized lithium metal powder is adopted, the use is not limited by the environment, the operation is simpler, and meanwhile, the stabilized lithium metal powder has a special positive temperature coefficient effect and can improve the safety of the battery.
Preferably, a ternary material of lithium iron phosphate, lithium manganate, lithium cobaltate, nickel cobalt aluminum or nickel cobalt manganese is used as a main material of the positive active material, and indium oxide, graphene, polystyrene sulfonate and a binder coated with polyaniline are used as auxiliary materials of the positive active material. In the technical scheme, the graphene oxide, the polystyrene sulfonate and the polyaniline-coated indium oxide are used as auxiliary materials of the positive active material, have high conductivity, high mechanical strength and corrosion resistance, and can improve the electronic conduction capability of the positive active material. Therefore, the polyaniline, the graphene oxide, the polystyrene sulfonate and the polyaniline-coated indium oxide are used as auxiliary materials of the positive active material, so that the performance of the battery can be improved, the corrosion resistance can be improved, and the service life of the lithium ion battery can be prolonged.
Preferably, the mass ratio of the main material to the auxiliary material is 3-5: the auxiliary material comprises, by weight, 30-35 parts of graphene oxide, 40-50 parts of polystyrene sulfonate, 10-15 parts of a binder and 40-45 parts of polyaniline-coated indium oxide.
Preferably, the preparation method of the polyaniline-coated indium oxide comprises the following steps: dissolving indium oxide in diethylene glycol to obtain a reaction system, slowly adding sodium hydroxide, stirring for 1-3h, heating to 140-160 ℃ within 2-2.5h, reacting for 1-3h, and cooling; washing the precipitate obtained by centrifugation with a mixed solution of ethanol and methyl acetate in a volume ratio of 1:2, acetone and deionized water in sequence, and drying in vacuum to obtain the nucleus-based nano indium oxide; then ultrasonically dispersing the base core nano-chlorine oxide in absolute ethyl alcohol, adding an absolute ethyl alcohol solution containing polyaniline, dropwise adding concentrated ammonia water, stirring and reacting for 1-1.5h at 85-95 ℃, washing precipitates obtained by centrifugal separation with absolute ethyl alcohol and deionized water in sequence, roasting and crushing to obtain polyaniline-coated nano-indium oxide.
Preferably, the preparation of the stabilized lithium metal powder with positive temperature coefficient effect comprises the following steps:
a) putting a 3 x 3cm lithium metal sheet into a reactor with a stirrer at room temperature under the atmosphere of dry argon flow, adding 1kg mineral oil, heating to 230 ℃ at 200-;
b) stirring the molten lithium metal obtained in the step a) at 8000rpm for 2-5min, and then cooling to 40 ℃ to obtain dispersed lithium metal;
c) dissolving 20g of conductive polymer in 50g of mineral oil, then adding the conductive polymer into the dispersed lithium metal obtained in the step b), stirring at 1000rpm for 15-20min, filtering in an argon atmosphere, washing with ethane for three times, and washing with n-pentane for one time; vacuum drying, pulverizing, sealing and storing.
Preferably, the conductive polymer is selected from the group consisting of polythiophene, poly 3-methylthiophene, poly 3-decylthiophene, poly 3-butylthiophene.
Preferably, the negative electrode material is a graphite-based, silicon-based, or alloy negative electrode-based material.
Preferably, the separator is polyethylene, polypropylene, polyimide or non-woven fabric coated with nano ceramic material on the surface. In the technical scheme, the safety performance of the lithium ion battery is improved by utilizing the characteristics of good thermal stability and mechanical property of the nano ceramic material, and meanwhile, the nano ceramic material is low in cost.
Preferably, the method for preparing the non-woven fabric coated with the nano ceramic material on the surface comprises the following steps: and spraying the nano ceramic material on the surface of the non-woven fabric by adopting a plasma spraying technology.
The invention has the beneficial effects that:
the improvement is carried out in the battery, the internal temperature change can be sensed in time, and because the layer of stabilized lithium metal powder is coated on the surface of the battery pole piece and the layer of metal powder is conductive, the electrochemical performance of the battery is not influenced, and simultaneously because the first effect of the battery can be improved, the energy density of the battery is not influenced, and the energy density of the battery can be improved; the stabilized lithium metal powder is adopted, the use is not limited by the environment, the operation is simpler, and meanwhile, the stabilized lithium metal powder has a special positive temperature coefficient effect and can improve the safety of the battery. The stabilized lithium metal powder with positive temperature coefficient effect is adopted, so that the energy density of the battery is improved, and the safety of the battery can be improved.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
The preparation of stabilized lithium metal powder with positive temperature coefficient effect comprises the following steps:
a) putting a 3 x 3cm lithium metal sheet into a reactor with a stirrer at room temperature under the atmosphere of dry argon flow, adding 1kg mineral oil, heating to 200 ℃, and stirring at 300rpm to obtain molten lithium metal;
b) stirring the molten lithium metal obtained in the step a) at 8000rpm for 2min, and then cooling to 40 ℃ to obtain dispersed lithium metal;
c) dissolving 20g of polythiophene into 50g of mineral oil, then adding into the dispersed lithium metal obtained in the step b), stirring at 1000rpm for 15min, filtering in an argon atmosphere, washing with ethane for three times, and washing with n-pentane for one time; vacuum drying, pulverizing, sealing and storing.
Preparing a negative plate: selecting natural graphite as a negative active material, and preparing the following raw materials in percentage by weight: conductive adhesive: and mixing the binder with solvent water according to the ratio of 95:1:4 to obtain negative electrode slurry, coating the negative electrode slurry on a current collector copper foil, and drying. And then mixing the stabilized lithium metal powder with the positive temperature coefficient effect with a binder according to the weight ratio of 95:5, dissolving in an NMP solvent, coating the obtained slurry on the surface of the prepared negative electrode, drying, rolling, and cutting to obtain the negative electrode sheet coated with the stabilized lithium metal powder.
Preparing a positive plate: the method comprises the steps of taking a ternary material of lithium iron phosphate, lithium manganate, lithium cobaltate, nickel cobalt aluminum or nickel cobalt manganese as a main material of a positive active material, taking indium oxide, graphene, polystyrene sulfonate and a binder coated with polyaniline as a secondary material of the positive active material, mixing positive slurry according to the weight ratio of the positive active material to a conductive agent to the binder of 90: 5, and uniformly coating the positive slurry on a positive base fluid aluminum foil. After drying, rolling by a rolling machine, and then slitting to prepare the positive pole piece. Wherein the mass ratio of the main material to the auxiliary material is 3: the auxiliary material comprises, by weight, 30 parts of graphene oxide, 40 parts of polystyrene sulfonate, 10 parts of a binder and 40 parts of polyaniline-coated indium oxide.
The preparation method of the indium oxide coated by polyaniline comprises the following steps: dissolving indium oxide in diethylene glycol to obtain a reaction system, slowly adding sodium hydroxide, stirring for 1h, heating to 140 ℃ within 2h, reacting for 1h, and cooling; washing the precipitate obtained by centrifugation with a mixed solution of ethanol and methyl acetate in a volume ratio of 1:2, acetone and deionized water in sequence, and drying in vacuum to obtain the nucleus-based nano indium oxide; then, ultrasonically dispersing the base-core nano-chlorine oxide in absolute ethyl alcohol, adding an absolute ethyl alcohol solution containing polyaniline, dropwise adding concentrated ammonia water, stirring and reacting for 1h at 85 ℃, washing precipitates obtained by centrifugal separation with absolute ethyl alcohol and deionized water in sequence, roasting and crushing to obtain polyaniline-coated nano-indium oxide.
Preparing a diaphragm: polyethylene was chosen as the separator.
Preparing electrolyte: selecting commercial LiPF6An electrolyte dissolved in an organic solution.
Preparing a battery: and preparing a battery core by laminating the positive and negative pole pieces and the diaphragm, packaging the battery core in an aluminum plastic film, injecting electrolyte, sealing and forming to obtain the lithium metal negative electrode battery.
Example 2
The preparation of stabilized lithium metal powder with positive temperature coefficient effect comprises the following steps:
a) putting a 3 x 3cm lithium metal sheet into a reactor with a stirrer at room temperature under the atmosphere of dry argon flow, adding 1kg mineral oil, heating to 220 ℃, and stirring at 400rpm to obtain molten lithium metal;
b) stirring the molten lithium metal obtained in the step a) at 8000rpm for 3min, and then cooling to 40 ℃ to obtain dispersed lithium metal;
c) dissolving 20g of poly-3-methylthiophene in 50g of mineral oil, then adding the solution to the dispersed lithium metal obtained in step b), stirring at 1000rpm for 18min, filtering in an argon atmosphere, washing with ethane for three times, and washing with n-pentane for one time; vacuum drying, pulverizing, sealing and storing.
Preparing a negative plate: lithium titanate is selected as a negative electrode active material, and the ratio of the active material: conductive adhesive: and mixing the binder with solvent water according to the ratio of 95:1:4 to obtain negative electrode slurry, coating the negative electrode slurry on a current collector copper foil, and drying. .
Preparing a positive plate: the method comprises the steps of taking a ternary material of lithium iron phosphate, lithium manganate, lithium cobaltate, nickel cobalt aluminum or nickel cobalt manganese as a main material of a positive active material, taking indium oxide, graphene, polystyrene sulfonate and a binder coated with polyaniline as a secondary material of the positive active material, mixing positive slurry according to the weight ratio of the positive active material to a conductive agent to the binder of 90: 5, and uniformly coating the positive slurry on a positive base fluid aluminum foil. And then mixing the stabilized lithium metal powder with the positive temperature coefficient effect with a binder according to the weight ratio of 95:5, dissolving in an NMP solvent, coating the obtained slurry on the surface of the prepared positive electrode, drying, rolling, and cutting to obtain the positive electrode sheet coated with the stabilized lithium metal powder. Wherein the mass ratio of the main material to the auxiliary material is 4: the auxiliary material comprises, by weight, 32 parts of graphene oxide, 45 parts of polystyrene sulfonate, 12 parts of a binder and 43 parts of polyaniline-coated indium oxide.
The preparation method of the indium oxide coated by polyaniline comprises the following steps: dissolving indium oxide in diethylene glycol to obtain a reaction system, slowly adding sodium hydroxide, stirring for 2 hours, heating to 150 ℃ within 2.5 hours, reacting for 2 hours, and cooling; washing the precipitate obtained by centrifugation with a mixed solution of ethanol and methyl acetate in a volume ratio of 1:2, acetone and deionized water in sequence, and drying in vacuum to obtain the nucleus-based nano indium oxide; then, ultrasonically dispersing the base-core nano-chlorine oxide in absolute ethyl alcohol, adding an absolute ethyl alcohol solution containing polyaniline, dropwise adding concentrated ammonia water, stirring and reacting for 1.5 hours at 90 ℃, washing precipitates obtained by centrifugal separation with absolute ethyl alcohol and deionized water in sequence, roasting and crushing to obtain polyaniline-coated nano-indium oxide.
Preparing a diaphragm: selecting non-woven fabrics coated with nano ceramic materials on the surfaces as the diaphragm. The manufacturing method of the non-woven fabric coated with the nano ceramic material on the surface comprises the following steps: and spraying the nano ceramic material on the surface of the non-woven fabric by adopting a plasma spraying technology.
Preparing electrolyte: selecting commercial LiPF6An electrolyte dissolved in an organic solution.
Preparing a battery: and preparing a battery core by laminating the positive and negative pole pieces and the diaphragm, packaging the battery core in an aluminum plastic film, injecting electrolyte, sealing and forming to obtain the lithium metal negative electrode battery.
Example 3
The preparation of stabilized lithium metal powder with positive temperature coefficient effect comprises the following steps:
a) putting a 3 x 3cm lithium metal sheet into a reactor with a stirrer at room temperature under the atmosphere of dry argon flow, adding 1kg mineral oil, heating to 230 ℃, and stirring at 700rpm to obtain molten lithium metal;
b) stirring the molten lithium metal obtained in the step a) at 8000rpm for 5min, and then cooling to 40 ℃ to obtain dispersed lithium metal;
c) dissolving 20g of poly-3-decylthiophene in 50g of mineral oil, then adding the solution into the dispersed lithium metal obtained in the step b), stirring at 1000rpm for 20min, filtering in an argon atmosphere, washing with ethane for three times, and washing with n-pentane for one time; vacuum drying, pulverizing, sealing and storing.
Preparing a negative plate: selecting graphite, silicon materials or alloy negative electrode materials as negative electrode active materials, and preparing a composite material by using the following raw materials in percentage by weight: conductive adhesive: and mixing the binder with solvent water according to the ratio of 95:1:4 to obtain negative electrode slurry, coating the negative electrode slurry on a current collector copper foil, and drying. And then mixing the stabilized lithium metal powder with the positive temperature coefficient effect with a binder according to the weight ratio of 95:5, dissolving in an NMP solvent, coating the obtained slurry on the surface of the prepared negative electrode, drying, rolling, and cutting to obtain the negative electrode sheet coated with the stabilized lithium metal powder.
Preparing a positive plate: the method comprises the steps of taking a ternary material of lithium iron phosphate, lithium manganate, lithium cobaltate, nickel cobalt aluminum or nickel cobalt manganese as a main material of a positive active material, taking indium oxide, graphene, polystyrene sulfonate and a binder coated with polyaniline as a secondary material of the positive active material, mixing positive slurry according to the weight ratio of the positive active material to a conductive agent to the binder of 90: 5, and uniformly coating the positive slurry on a positive base fluid aluminum foil. And then mixing the stabilized lithium metal powder with the positive temperature coefficient effect with a binder according to the weight ratio of 95:5, dissolving in an NMP solvent, coating the obtained slurry on the surface of the prepared positive electrode, drying, rolling, and cutting to obtain the positive electrode sheet coated with the stabilized lithium metal powder. Wherein the mass ratio of the main material to the auxiliary material is 5: the auxiliary material comprises, by weight, 35 parts of graphene oxide, 50 parts of polystyrene sulfonate, 15 parts of a binder and 45 parts of polyaniline-coated indium oxide.
The preparation method of the indium oxide coated by polyaniline comprises the following steps: dissolving indium oxide in diethylene glycol to obtain a reaction system, slowly adding sodium hydroxide, stirring for 3h, heating to 160 ℃ within 2.5h, reacting for 3h, and cooling; washing the precipitate obtained by centrifugation with a mixed solution of ethanol and methyl acetate in a volume ratio of 1:2, acetone and deionized water in sequence, and drying in vacuum to obtain the nucleus-based nano indium oxide; then, ultrasonically dispersing the base-core nano-chlorine oxide in absolute ethyl alcohol, adding an absolute ethyl alcohol solution containing polyaniline, dropwise adding concentrated ammonia water, stirring and reacting for 1.5 hours at 95 ℃, washing precipitates obtained by centrifugal separation with absolute ethyl alcohol and deionized water in sequence, roasting and crushing to obtain polyaniline-coated nano-indium oxide.
Preparing a diaphragm: polypropylene was chosen as the separator.
Preparing electrolyte: selecting commercial LiPF6An electrolyte dissolved in an organic solution.
Preparing a battery: and preparing a battery core by laminating the positive and negative pole pieces and the diaphragm, packaging the battery core in an aluminum plastic film, injecting electrolyte, sealing and forming to obtain the lithium metal negative electrode battery.
Tests show that the first efficiency of the battery reaches 98%, and the energy density of the battery can reach 300 Wh/kg. The first efficiency and the energy density of the existing battery are obviously improved. And the battery can pass safety tests such as overcharge, overdischarge, needling and extrusion, and the like, so that the battery has very good safety performance.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (6)
1. A high-safety high-energy-density lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode and the negative electrode are separated by the diaphragm, a battery cell is formed by winding or laminating, the battery cell is packaged into a battery shell, the electrolyte is injected into the battery shell, and the battery is sealed, so that the battery is obtained; lithium iron phosphate, lithium manganate, lithium cobaltate, nickel cobalt aluminum lithium ternary material or nickel cobalt manganese lithium ternary material is used as a main material of the positive active material, and indium oxide, graphene oxide, polystyrene sulfonate and a binder coated by polyaniline are used as auxiliary materials of the positive active material; the preparation of stabilized lithium metal powder with positive temperature coefficient effect comprises the following steps:
a) putting a 3 x 3cm lithium metal sheet into a reactor with a stirrer at room temperature under the atmosphere of dry argon flow, adding 1kg mineral oil, heating to 230 ℃ at 200-;
b) stirring the molten lithium metal obtained in the step a) at 8000rpm for 2-5min, and then cooling to 40 ℃ to obtain dispersed lithium metal;
c) dissolving 20g of conductive polymer in 50g of mineral oil, then adding the conductive polymer into the dispersed lithium metal obtained in the step b), stirring at 1000rpm for 15-20min, filtering in an argon atmosphere, washing with ethane for three times, and washing with n-pentane for one time; vacuum drying, pulverizing, and storing in sealed condition;
the conductive polymer is selected from one or more of polythiophene, poly 3-methylthiophene, poly 3-decylthiophene and poly 3-butylthiophene.
2. The high-safety high-energy-density lithium ion battery according to claim 1, wherein the mass ratio of the main material to the auxiliary material of the positive electrode active material is 3-5: the auxiliary material of the positive active material comprises, by weight, 30-35 parts of graphene oxide, 40-50 parts of polystyrene sulfonate, 10-15 parts of a binder and 40-45 parts of polyaniline-coated indium oxide.
3. The high-safety high-energy-density lithium ion battery according to claim 1 or 2, wherein the preparation method of the polyaniline-coated indium oxide comprises the following steps: dissolving indium oxide in diethylene glycol to obtain a reaction system, slowly adding sodium hydroxide, stirring for 1-3h, heating to 140-160 ℃ within 2-2.5h, reacting for 1-3h, and cooling; washing the precipitate obtained by centrifugation with a mixed solution of ethanol and methyl acetate in a volume ratio of 1:2, acetone and deionized water in sequence, and drying in vacuum to obtain the nucleus-based nano indium oxide; then, ultrasonically dispersing the base core nano indium oxide in absolute ethyl alcohol, adding an absolute ethyl alcohol solution containing polyaniline, dropwise adding concentrated ammonia water, stirring and reacting for 1-1.5h at 85-95 ℃, washing precipitates obtained by centrifugal separation with absolute ethyl alcohol and deionized water in sequence, roasting and crushing to obtain polyaniline-coated nano indium oxide.
4. The high safety type high energy density lithium ion battery according to claim 1, wherein the negative electrode material is graphite, silicon material or alloy negative electrode material.
5. The high-safety high-energy-density lithium ion battery according to claim 1, wherein the separator is polyethylene, polypropylene, polyimide or non-woven fabric coated with nano ceramic material on the surface.
6. The high-safety high-energy-density lithium ion battery according to claim 5, wherein the non-woven fabric with the surface coated with the nano-ceramic material is prepared by the following steps: and spraying the nano ceramic material on the surface of the non-woven fabric by adopting a plasma spraying technology.
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CN109802140A (en) * | 2018-12-21 | 2019-05-24 | 上海力信能源科技有限责任公司 | A kind of lithium battery cathode pole piece and preparation method thereof |
KR102462952B1 (en) * | 2019-04-10 | 2022-11-04 | 주식회사 엘지화학 | Positive electrode active material for secondary battery, method for preparing the same and lithium secondary battery comprising the same |
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CN112467314A (en) * | 2020-11-03 | 2021-03-09 | 东莞市创明电池技术有限公司 | Thermosensitive material, electrode and preparation method thereof, and lithium secondary battery |
CN114583176B (en) * | 2022-05-06 | 2022-09-02 | 华中科技大学 | Multifunctional conductive agent and application thereof in pre-lithiation composite positive electrode |
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