CN102439771A - Porous conductive active composite electrode used in lithium ion battery - Google Patents
Porous conductive active composite electrode used in lithium ion battery Download PDFInfo
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- CN102439771A CN102439771A CN2011800013218A CN201180001321A CN102439771A CN 102439771 A CN102439771 A CN 102439771A CN 2011800013218 A CN2011800013218 A CN 2011800013218A CN 201180001321 A CN201180001321 A CN 201180001321A CN 102439771 A CN102439771 A CN 102439771A
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M10/052—Li-accumulators
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
Abstract
Active composite materials are diffused in a conductive porous matrix, and the conductive porous matrix is formed on a current collector to form a composite lithium ion battery electrode. The active composite materials comprise nanocluster active materials diffused on a conductive skeleton structure, the conductive skeleton structure comprises a conductive polymer or a conductive fibril. The active materials are metal base materials comprising one or more elements, such as tin, aluminum, silicon, titanium; or carbon base materials comprising one or more carbon materials, such as graphite, carbon fiber, carbon nanotube; or a combination of the metal base materials and the carbon base materials. The particle size of the active material is between 1 nanometer to 10 micrometers. By an in-situ polymerization method or a chemical graft method, the active materials are diffused in the conductive skeleton. The conductive porous matrix comprises a conductive polymer adhesive and a lithium ion diffusion channel generated by a pore forming agent, and conductive particles.
Description
[technical field]
The present invention relates to the electrode of lithium ion battery, particularly comprise the electrode of active composite material; This active composite material is dispersed in the conductivity porous matrix; There is passage to be used for the lithium ion diffusion in this conductivity porous matrix.
[background technology]
Lithium ion battery is used for multiple portable electric appts, like mobile phone and laptop computer.Although the enough competent portable electric appts that is used for of lithium ion battery, tomorrow requirement comprise the capacitance that the battery that is used for electric motor car will be higher than those conventional battery needs.There has been the whole bag of tricks to be used to improve the specific capacity of lithium ion battery material; Such as the open text 2011/0114254,2008/0237536,2010/0021819,2010/0119942,2010/0143798,2010/0285365,2010/0062338 of United States Patent (USP), and loose structure anode and the composite anode described in International Publication WO 2008/021961 and the European patent 1 207 572.Though these anodes can improve battery performance; But still have and need seek to improve the lithium ion cell electrode performance and take into account the technology that processing procedure is simple, low-cost and can produce in batches simultaneously, with can supply future the demand of electric motor car and portable electric appts on a large scale.
[summary of the invention]
The present invention relates to the composite lithium ion cell electrode, it contains an active composite material and is dispersed in the conductivity porous matrix, and this conductivity porous matrix is formed on the collector.The active material that this active composite material contains nanocluster is dispersed on the conducting matrix grain structure.This active material is atomic tin, aluminium, silicon, titanium and carbon, and its particle size is between about 1 nanometer to 10 micron.The electric conductivity skeleton comprises an at least one conducting polymer or a conduction fibril.Through in-situ polymerization or chemical graft method, active material is dispersed on the conducting matrix grain.
The conductivity porous matrix comprises an electric conductive polymer adhesive and lithium ion diffusion admittance; This passage is formed by pore creating material during in active composite material is blended in the conductivity porous matrix.This conductivity porous matrix also comprises electroconductive particle.
[description of drawings]
Fig. 1 is the sketch map of the composite lithium ion cell electrode of one embodiment of the invention.
Fig. 2 is the sketch map that is used for the active composite material of Fig. 1 electrode.
[embodiment]
Referring to Fig. 1, show composite lithium ion cell electrode 10 of the present invention.In the embodiment shown in fig. 1, electrode comprises collector 20 (current collector), and it is conductive metal sheet such as copper normally.Place on the collector 20 is that an active composite material 30 is dispersed in a conductivity porous matrix 40.This active composite material comprises particulate active material 32, and is as shown in Figure 2, is dispersed on the conductivity skeleton structure 34.Active material 32 has the particulate structure, and its granular size scope is between about 1 nanometer is to about 10 microns.When this electrode was used as anode, particle comprised metal_based material such as tin, aluminium, silicon, titanium, or carbon-based material such as graphite, carbon fiber, CNT (CNT), perhaps combinations thereof.In anode, these materials are that lithium ion provides super embedding medium (intercalation media) in the charging stage.At discharge regime, lithium ion moves to negative electrode from anode.Because in the embedding of lithium ion with the change in volume that causes during deviating from, behind charging that repeats and discharge cycle, the solid metal active material can produce fragmentation (being cleaved into littler particle).Using the benefit of nanometer particle active material is to avoid this problem, also can provide a bigger surface area to be used for embedding lithium (lithium intercalation).
The conducting polymer of conductivity skeleton 34 comprises pyrroles (pyrrole), aniline (aniline), thiophene (thiofuran); Perhaps conducting electricity fibril such as CNT or carbon nano-fiber also can be used as skeleton 34.Can see that from Fig. 2 skeleton 34 and the structure tool microchannel that the active material that disperses 32 forms provide the lithium ion diffusion admittance to active material 32.Lithium ion embeds to be increased, thereby the capacitance of battery just is improved through this active composite material 30.At charging and interdischarge interval, when lithium ion embedded and deviates from, the microchannel also helped for the expansion of active material particles and contraction the space to be provided.
Active composite material 30 is dispersed in the conductivity porous matrix 40, and is as shown in Figure 1.Conductivity porous matrix 40 comprises an electric conductive polymer adhesive (polymeric binder) and lithium ion diffusion admittance 42, this passage in active composite material is blended in the conductivity porous matrix during by pore-creating material production (following will the discussion).The electric conductive polymer adhesive can be a kind of improved pyrroles, aniline or thiophene, or other suitable electric conductive polymers, and the tool conductance is higher than the material of 10S/cm.Lithium ion passage 42 provides lithium to be moved to the path of interior active material 32 by electrode surface.In addition, at charging and interdischarge interval, when lithium ion embedded and deviates from, passage 42 helped for the expansion of whole active electrode and contraction the space to be provided.At an embodiment, the cumulative volume of passage is less than 5% of electrode.
In order to increase the conductivity of porous matrix 40, at least a electroconductive particle such as particle 50 or 60 are comprised in the conductivity porous matrix.In the embodiment of Fig. 1, particle 50 is a graphite, and particle 60 is carbon black (carbon black).But, also can select other electroconductive particles to be used in the porous matrix 40.
A typical method of making electrode 10 is described below.The formation of active composite material 30 comprises from a kind of suitable precursor solution (precursor solution) separates out active material 32 like tin, aluminium, silicon or titanium like deposition tin, aluminium, silicon or the titanium precursor body salt (nitrate, carbonate etc.).Precursor solution is mixed in additive such as sulfonate (sulfonate), imines (imine) and nitride (nitride).The precursor powder that dehydrates then and obtain precipitating, its particle size approximately is the 1-100 micron.Then, this sediment is heat-treated being lower than in 1000 ℃ air or the inert environments, produce reduction/calcined powder, understand after the grinding that particle size is reduced to less than in 100 microns the scope, preferably in the scope of 1 nanometer to 10 micron.This method tool meets cost benefit, transreplication and can produce feasibility in batches.
For active material 32 is dispersed on the skeleton structure 34, can select to use several method.One of them method is, carbon fiber, CNT and/or carbon-point are carried out surface treatment, (COOH) ties up on the carbon back skeleton and produce a carboxyl.The active material particulate mixes with additive; Like APTES (aminopropyltriethoxywerene werene), APTMS (3-aminopropyltriethoxywerene werene) or APPA (2-amino-5-phosphine-3-penetenoic acid), again through rinsing with the formation activation of dry back active material powder.In order to form carboxyl on the carbon skeleton structure, with a carbon skeleton structure and a reagent mix, like EDC (N-(3-dimethylamino-propyl)-N '-ethyl-carbodiimide hydrochloride) or NHS (N-hydroxy-succinamide sulfonate sodium).This has the carbon skeleton structure of carboxyl to carry out chemical action with the solution of this activating activities material powder through mixing, and this active material is combined on this carbon back skeleton.
Active material is dispersed in the embodiment on the skeleton at another, has used situ aggregation method.Particulate tin, aluminium, silicon or titanium mix with an additive, like sulfonic acid, sodium salt or sulfonate.This mixture is added to one and contains polymer solution, like pyrroles, aniline, thiophene.Add an additive such as ferric trichloride or ammonium sulfate again.In a deoxidation solution, be lower than under about 10 ℃ temperature polymerization reaction take place.The active composite material that produces is exactly that active material is dispersed on the stephanoporate framework.
Earlier atomic active material is dispersed on the skeleton to prepare an active material compound, incorporates the active material compound into the conductivity porous matrix then, so active material particles can conglomerate, and thereby improves the area that is used for the embedding lithium.In order to set up the conductivity porous matrix, obtain an adhesive by a conducting polymer such as pyrroles, aniline or thiophene surface modification (surface-modified); (it can be pore-creating material and/or expanded material such as carbonate, (NH with this active material compound, conductive polymer adhesive and a pore creating material
4)
2CO
3Or C
2H
4N
4O
2), and other electroconductive particle such as particle 50 and/or 60 (graphite, carbon black) mix.With this mixture apply collector 20 like copper sheet on, through bleed with the solvent evaporation after, stay active material compound and electroconductive particle and be dispersed in the porous, electrically conductive matrix; The pore-creating material forms hole and produces continuous interconnection duct in matrix, be provided as the passage that lithium ion moves.
Though described each embodiment of the present invention, be not limited in these embodiment.Various variations and change will be understood by those skilled in the art.These variations and change are included in the scope of accompanying claims.
Claims (15)
1. a composite lithium ion cell electrode comprises
One active composite material is dispersed in the conductivity porous matrix, and this conductivity porous matrix is formed on the collector; This active composite material comprises that an active material is dispersed on the conductivity skeleton structure, and the atomic granular size of active material comprises following at least a material less than 10 microns: a metal_based material comprises one or more elements such as tin, aluminium, silicon, titanium; Perhaps a carbon-based material comprises one or more carbon materials such as graphite, carbon fiber, CNT; The perhaps composition of this metal_based material and this carbon-based material; The conductivity skeleton comprises an at least one conducting polymer or a conduction fibril; Through a situ aggregation method or a chemical graft process, said active material is dispersed on the said conductivity skeleton;
Said conductivity porous matrix comprises an electric conductive polymer adhesive and lithium ion diffusion admittance; Its passage in active composite material is blended in the conductivity porous matrix during form by pore creating material, said conductivity porous matrix also comprises the conducting particles of particulate.
2. composite lithium ion cell electrode as claimed in claim 1, wherein said collector are copper sheets.
3. composite lithium ion cell electrode as claimed in claim 1, wherein said conducting particles are carbon black and/or graphite.
4. composite lithium ion cell electrode as claimed in claim 1, wherein said conductivity skeleton is a carbon fiber and/or CNT.
5. composite lithium ion cell electrode as claimed in claim 1, wherein said conductivity skeleton is an electric conductive polymer.
6. composite lithium ion cell electrode as claimed in claim 1, wherein said electrode is an anode.
7. composite lithium ion cell electrode as claimed in claim 1, wherein said electric conductive polymer adhesive comprises pyrroles, aniline or thiophene.
8. composite lithium ion cell electrode as claimed in claim 1, wherein said pore creating material comprise at least one pore-creating material or expanded material.
9. method of making the described composite lithium ion cell electrode of claim 1; Comprise: deposition is separated out one or more elements and is comprised tin, aluminium, silicon or titanium from the precursor solution of a kind of tin, aluminium, silicon or titanium precursor body salt or its mixture, forms the Metal Substrate active material; Said precursor solution mixes with following one or more additives: sulfonate, imines and nitride; Sediment dehydrates and the precursor powder that obtains precipitating; Its particle size is the 1-100 micron; Then; This sediment is heat-treated being lower than in 1000 ℃ air or the inert environments, obtain reducing the active material powder of calcining, after further grinding the active material particles size is reduced to less than 100 microns.
10. method of making the described composite lithium ion cell electrode of claim 1, wherein the active material particles size is in the scope of 1 nanometer to 10 micron.
11. a method of making the described composite lithium ion cell electrode of claim 1 comprises: framework material and a reagent are reacted, form carboxyl on this framework material, this framework material comprises carbon fiber, CNT or carbon-point; The active material particulate mixes with one or more additives, with form an activation active material; This framework material with carboxyl produces chemical effect with the solution of this activating activities material powder through mixing then, and this active material is combined on this framework material.
12. a method of making the described composite lithium ion cell electrode of claim 1 comprises: mixed active particles of material is in the polymeric solution of a conducting polymer, to disperse this active material on the conductivity skeleton.
13. method as claimed in claim 12, wherein said conducting polymer comprises pyrroles, aniline or thiophene.
14. a method of making the described composite lithium ion cell electrode of claim 1 comprises:, form active composite material through active material being dispersed on the conductivity skeleton; Said active composite material is added in the mixture, and this mixture comprises a conductive polymer adhesive, obtains this conductive polymer adhesive by a conducting polymer through surface modification; This mixture also comprises a pore creating material, and its material is pore-creating material or expanded material or its combination; This mixture also comprises conducting particles; This mixture is applied on collector, and to form a porous, electrically conductive matrix, active composite material and conducting particles are dispersed in wherein.
15. method as claimed in claim 14, wherein said conducting polymer comprises pyrroles, aniline or thiophene.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2011/078672 WO2013026190A1 (en) | 2011-08-19 | 2011-08-19 | Porous conductive active composite electrode for lithium ion batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102439771A true CN102439771A (en) | 2012-05-02 |
| CN102439771B CN102439771B (en) | 2014-04-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180001321.8A Expired - Fee Related CN102439771B (en) | 2011-08-19 | 2011-08-19 | Porous conductive active composite electrode used in lithium ion battery |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN102439771B (en) |
| HK (1) | HK1173558A1 (en) |
| WO (1) | WO2013026190A1 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103904299A (en) * | 2014-03-24 | 2014-07-02 | 宁德新能源科技有限公司 | Lithium-ion secondary battery and negative pole piece thereof |
| US9431651B2 (en) | 2013-08-30 | 2016-08-30 | Hong Kong Applied Science and Technology Research Institute Company Limited | Composite material for a lithium ion battery anode and a method of producing the same |
| CN106663812A (en) * | 2014-09-08 | 2017-05-10 | Jsr株式会社 | Binder composition for storage device electrode, slurry for storage device electrode, storage device electrode, and storage device |
| CN106861762A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | The synthesis of metal oxide nano cluster and nano-cluster and the application in water oxygen |
| CN109205743A (en) * | 2018-11-02 | 2019-01-15 | 南京工业大学 | A kind of preparation method and applications of carbon nanotube composite titanium oxide porous carbon materials |
| CN109473633A (en) * | 2017-09-07 | 2019-03-15 | 上海杉杉科技有限公司 | A kind of lithium ion cell nano silicon substrate composite fibre negative electrode material and preparation method thereof |
| CN109509877A (en) * | 2018-11-30 | 2019-03-22 | 清华大学深圳研究生院 | Carbon coating porous metal coating collector, preparation method and lithium battery |
| CN109950464A (en) * | 2019-02-01 | 2019-06-28 | 湖北锂诺新能源科技有限公司 | A kind of porous silicon-carbon cathode pole piece and preparation method thereof |
| CN113278820A (en) * | 2021-05-21 | 2021-08-20 | 中南大学 | Electrode material for lithium extraction in salt lake and preparation method and application thereof |
| CN115312777A (en) * | 2022-09-07 | 2022-11-08 | 湖北亿纬动力有限公司 | Low-tortuosity thick electrode and preparation method and application thereof |
| WO2023165593A1 (en) * | 2022-03-03 | 2023-09-07 | 比亚迪股份有限公司 | Electrode plate and preparation method therefor, and lithium battery |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108666568A (en) * | 2017-04-01 | 2018-10-16 | 清华大学 | Anode of lithium ion battery |
| KR102203515B1 (en) * | 2020-02-28 | 2021-01-14 | 서울대학교산학협력단 | Method of preparing electrodes for lithium secondary battery |
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| CN101894940A (en) * | 2010-08-03 | 2010-11-24 | 哈尔滨工业大学 | Porous silicon-based cathode for lithium battery and preparation method thereof |
| US20110123858A1 (en) * | 2008-07-28 | 2011-05-26 | Hydro-Quebec | Composite electrode material |
-
2011
- 2011-08-19 WO PCT/CN2011/078672 patent/WO2013026190A1/en active Application Filing
- 2011-08-19 CN CN201180001321.8A patent/CN102439771B/en not_active Expired - Fee Related
-
2012
- 2012-10-30 HK HK12110826.5A patent/HK1173558A1/en not_active IP Right Cessation
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| CN101009368A (en) * | 2001-03-20 | 2007-08-01 | 爱克索里奥克斯公司 | Mesoporous network electrode for electrochemical cell |
| CN101499522A (en) * | 2008-01-28 | 2009-08-05 | 财团法人工业技术研究院 | Anode material of lithium battery and its production method, lithium secondary battery employing the same |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9431651B2 (en) | 2013-08-30 | 2016-08-30 | Hong Kong Applied Science and Technology Research Institute Company Limited | Composite material for a lithium ion battery anode and a method of producing the same |
| CN103904299B (en) * | 2014-03-24 | 2015-10-28 | 宁德新能源科技有限公司 | Lithium rechargeable battery and cathode pole piece thereof |
| CN103904299A (en) * | 2014-03-24 | 2014-07-02 | 宁德新能源科技有限公司 | Lithium-ion secondary battery and negative pole piece thereof |
| CN106663812A (en) * | 2014-09-08 | 2017-05-10 | Jsr株式会社 | Binder composition for storage device electrode, slurry for storage device electrode, storage device electrode, and storage device |
| US10403896B2 (en) | 2014-09-08 | 2019-09-03 | Jsr Corporation | Binder composition for storage device electrode, slurry for storage device electrode, storage device electrode, and storage device |
| CN106861762B (en) * | 2015-12-12 | 2019-03-22 | 中国科学院大连化学物理研究所 | The synthesis of metal oxide nano cluster and nano-cluster and the application in water oxygen |
| CN106861762A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | The synthesis of metal oxide nano cluster and nano-cluster and the application in water oxygen |
| CN109473633A (en) * | 2017-09-07 | 2019-03-15 | 上海杉杉科技有限公司 | A kind of lithium ion cell nano silicon substrate composite fibre negative electrode material and preparation method thereof |
| CN109205743A (en) * | 2018-11-02 | 2019-01-15 | 南京工业大学 | A kind of preparation method and applications of carbon nanotube composite titanium oxide porous carbon materials |
| CN109205743B (en) * | 2018-11-02 | 2021-04-13 | 南京工业大学 | Preparation method and application of carbon nanotube composite titanium oxide porous carbon material |
| CN109509877A (en) * | 2018-11-30 | 2019-03-22 | 清华大学深圳研究生院 | Carbon coating porous metal coating collector, preparation method and lithium battery |
| CN109950464A (en) * | 2019-02-01 | 2019-06-28 | 湖北锂诺新能源科技有限公司 | A kind of porous silicon-carbon cathode pole piece and preparation method thereof |
| CN113278820A (en) * | 2021-05-21 | 2021-08-20 | 中南大学 | Electrode material for lithium extraction in salt lake and preparation method and application thereof |
| WO2023165593A1 (en) * | 2022-03-03 | 2023-09-07 | 比亚迪股份有限公司 | Electrode plate and preparation method therefor, and lithium battery |
| CN115312777A (en) * | 2022-09-07 | 2022-11-08 | 湖北亿纬动力有限公司 | Low-tortuosity thick electrode and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013026190A1 (en) | 2013-02-28 |
| HK1173558A1 (en) | 2013-05-16 |
| CN102439771B (en) | 2014-04-09 |
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