CN105603494A - Electrophoretic deposition system and method for preparing silicon-based anode material of lithium ion battery - Google Patents
Electrophoretic deposition system and method for preparing silicon-based anode material of lithium ion battery Download PDFInfo
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- CN105603494A CN105603494A CN201610056922.3A CN201610056922A CN105603494A CN 105603494 A CN105603494 A CN 105603494A CN 201610056922 A CN201610056922 A CN 201610056922A CN 105603494 A CN105603494 A CN 105603494A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/02—Electrophoretic coating characterised by the process with inorganic material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/04—Electrophoretic coating characterised by the process with organic material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
- C25D13/16—Wires; Strips; Foils
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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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides an electrophoretic deposition system and a method for preparing a silicon-base anode material of a lithium ion battery. A reel-to-reel continuous operation system is adopted as the electrophoretic deposition system. The electrophoretic deposition system comprises an electrophoretic electrodeposition system, a material supplying system, a material recycling system and an electronic control system, wherein the material supplying system and the material recycling system are communicated with the electrophoretic electrodeposition system, and the material supplying system supplies electrophoretic liquid; the electrophoretic electrodeposition system comprises a deposition pool which is provided with an unreeling opening and a reeling opening, the unreeling opening and the reeling opening are provided with pulleys which are used for conveying a copper foil base material, and the copper foil base material serves as a working electrode to be connected with a positive electrode of a power supply; the material recycling system recycles the electrophoretic liquid which completes electrophoretic deposition; the electronic control system is connected with the electrophoretic electrodeposition system and controls operation of the electrophoretic electrodeposition system. Through the electrophoretic deposition system, continuity of preparation of the silicon-based anode material of the lithium ion battery can be achieved, the technological process is simple, the mechanical degree is high, and the electrophoretic deposition system is suitable for industrial mass production.
Description
Technical field
The present invention relates to technical field prepared by lithium ion battery negative material, specially refer to one and prepareThe method of silicon based anode material for lithium ion battery.
Background technology
Lithium ion battery in the eighties in last century enter practical since, because it has, specific energy is high, battery is electricPress the advantages such as high, operating temperature range is wide, storage life is long, be widely used in military and civilian small electricalIn device, as portable computer, camera, electric tool etc. But along with social development, outstandingIt is the fast development of ev industry, and the lithium ion battery of research and development high-energy-density is extremely urgent. Negative poleAs an indispensable part for lithium ion battery, the lithium ion battery negative of research and development high-energy-density is also aobviousObtain most important.
Commercial lithium ion battery negative material is mainly graphite-like material with carbon element at present, but graphite-like material with carbon elementTheoretical specific capacity be only 372mAh/g, cannot meet the requirement of lithium ion battery with high energy density negative pole. SiliconAs a kind of emerging li-ion electrode negative material, there is very high theoretical specific capacity (4200mAh/g),And its discharge platform, a little more than carbon class material, in impulse electricity process, is difficult for forming Li dendrite, thereby improvesThe security performance of battery. But silicon because volumetric expansion is shunk acutely, can cause material in cyclic processEfflorescence and losing connects with the electrochemistry of conductive substrates, causes the most at last the rapid decay of capacity. By silicon substrateIt is the effective way that suppresses volumetric expansion, prevents efflorescence that material carries out micro-nano-scale processing, in addition, and by silicon materialIt is compound with Graphene again that material covers carbon, can reduce the efflorescence of material, is conducive to improve the cyclicity of silicon-based anodeEnergy. But micro-nano-scale silica-base material specific area after treatment is large, dispersed and difficult. PatentCN103050672A has invented a kind of method that adopts suction filtration and has prepared Graphene-silicon combination electrode, but workSkill process is loaded down with trivial details, is unfavorable for commercialization, and the cycle performance of electrode is not good.
Summary of the invention
The object of the present invention is to provide a kind of electrophoretic deposition system, is volume to volume continous way operating system, profitPrepare Silicon Based Anode Materials for Lithium-Ion Batteries by this system, technological process is simple, and mechanization degree is high, is suitable forIn industrial production in enormous quantities.
For this reason, the present invention is by the following technical solutions:
A kind of electrophoretic deposition system, is volume to volume continous way operating system, comprises electrophoretic deposition system, dividesThe feeding system and the material recovery system that are not connected with electrophoretic deposition system, and electric-control system, wherein
Feeding system, provides electrophoresis liquid;
Electrophoretic deposition system, comprises sedimentation basin, is provided with and unreels mouth and rolling mouth, institute on described sedimentation basinState and unreel mouthful and rolling mouth is provided with pulley, described pulley is used for transmitting copper foil base material, and described copper foil base material is workMake electrode, connect positive source;
Material recovery system, reclaims the electrophoresis liquid after electrophoretic deposition completes;
Electric-control system, connects the running of controlling electrophoretic deposition system.
Preferably, described electrophoretic deposition system is also provided with the square to electrode of two isolation symmetries, connects power supplyNegative pole; The described pulley that unreels mouth and rolling mouth rotates and drives copper foil base material square between electrode by two.
Preferably, described positive source is column roller, described electrophoretic deposition system be also provided with power supply justExtremely symmetrical U-shaped groove structure to electrode, connect power cathode.
Preferably, the column roller of described copper foil base material rolled power positive pole connects and unreels mouthful and rolling mouth is provided withPulley, described pulley is consistent with the rotation direction of column roller, and drives the rotation of copper foil base material.
The present invention also provides a kind of and utilizes above-mentioned electrophoretic deposition system to prepare Silicon Based Anode Materials for Lithium-Ion BatteriesMethod, comprises as follows:
1) open electric-control system, drive the pulley on electrophoretic deposition pond, unreel copper foil base material as in tiselius apparatus;
2) open feeding system and make electrophoresis liquid enter electrophoretic deposition pond, wherein electrophoresis liquid is nano silicon material, carbonMaterial, cover carbon matrix precursor and dispersant be placed in decentralized medium dispersed become; Power-on, carries out electrophoresisDeposition obtains silico-carbo composite on copper foil base material; Powered-down, material recovery system recoveries electrophoresis liquid,Drive pulley rolling is the copper foil base material of depositing silicon-carbon composite, copper foil base material relative displacement, new Copper FoilBase material is moved in sedimentation basin;
3) open feeding system and make electrophoresis liquid enter electrophoretic deposition pond, repeat 2) operation, make a certain amount ofOn copper foil base material, all deposit and obtain silico-carbo composite;
4) silico-carbo composite is peeled off and is dried processing from copper foil base material, drier silico-carbo is multipleCondensation material is carbonization treatment in inert atmosphere, obtains lithium ion battery silico-carbo negative material.
Preferably, described nano silicon material comprises pure nano-silicon or nano silicon oxide, is preferably nano-silicon,Its diameter is 10-2000nm.
Preferably, described material with carbon element comprise CNT, carbon nano-fiber, nano carbon microsphere, Graphene orGraphene oxide, is preferably graphene oxide.
Preferably, described in, cover carbon matrix precursor for dissolving in decentralized medium and having after high-temperature calcination in inert atmosphereThe polymer of certain carbon residue, comprises glucose, polyoxyethylene, polyethylene glycol, polyvinyl alcohol, phenolic resinsOr at least one in epoxy resin, is preferably polyethylene glycol.
Preferably, described decentralized medium be water, acetone, ethanol, acetylacetone,2,4-pentanedione, cyclohexane, isopropyl alcohol,At least one in acetic acid, carrene, methyl ethyl ketone or toluene; Described dispersant be citric acid,Policapram, polyacrylamide, ethyoxyl alkyl sodium sulphate, α-sodium olefin sulfonate, lauryl sodium sulfate,At least one in ethyoxyl alkyl ammonium sulfate or iodine.
Preferably, described inert atmosphere is at least one in nitrogen, argon gas or hydrogen; Described carbonization placeThe temperature of reason is 400-1000 DEG C, is preferably 700 DEG C; Time is 0.5-20h, is preferably 4h.
The present invention adopts above technical scheme, and design electrophoretic deposition system is volume to volume continued operation system, profitCan realize continuity prepared by Silicon Based Anode Materials for Lithium-Ion Batteries by this system, technological process is simple, machineTool degree is high, is applicable to industrialized production in enormous quantities.
Brief description of the drawings
Fig. 1 is the module diagram of electrophoretic deposition system of the present invention.
Fig. 2 is the structural representation of the embodiment of the present invention one electrophoretic deposition system.
Fig. 3 is the structural representation of the embodiment of the present invention two electrophoretic deposition systems.
Detailed description of the invention
In order to make object of the present invention, feature and advantage more clear, below in conjunction with drawings and Examples,The specific embodiment of the present invention is made to more detailed explanation, in the following description, set forth a lotConcrete details is so that understand fully the present invention, but the present invention can be to be much different from its of descriptionHe implements mode. Therefore, the present invention is not subject to the restriction of the concrete enforcement of following discloses.
Embodiment mono-
A kind of electrophoretic deposition system, is volume to volume continous way operating system, as shown in Figure 1, comprises that electrophoresis electricity is heavyLong-pending system, the feeding system and the material recovery system that are connected with electrophoretic deposition system respectively, and automatically controlledSystem, wherein
Feeding system, provides electrophoresis liquid;
Electrophoretic deposition system, as shown in Figure 2, comprises sedimentation basin 1, on described sedimentation basin 1, is provided with and unreelsMouthful and rolling mouth, described in unreel mouth and rolling mouth is provided with pulley 2, described pulley 2 is for transmitting copper foil base material 3,Described copper foil base material 3 is working electrode, connects positive source; Wherein said electrophoretic deposition system is also provided with twoIndividual the square to electrode 4 of symmetry of isolating, connects power cathode; The described pulley 2 that unreels mouth and rolling mouth rotatesDrive copper foil base material 3 square between electrode 4 by two;
Material recovery system, reclaims the electrophoresis liquid after electrophoretic deposition completes;
Electric-control system, connects the running of controlling electrophoretic deposition system.
Embodiment bis-
A kind of electrophoretic deposition system, is volume to volume continous way operating system, as shown in Figure 1, comprises that electrophoresis electricity is heavyLong-pending system, the feeding system and the material recovery system that are connected with electrophoretic deposition system respectively, and automatically controlledSystem, wherein
Feeding system, provides electrophoresis liquid;
Electrophoretic deposition system, as shown in Figure 3, comprises sedimentation basin 1, on described sedimentation basin 1, is provided with and unreelsMouthful and rolling mouth, described in unreel mouth and rolling mouth is provided with pulley 2, described pulley 2 is for transmitting copper foil base material 3,Described copper foil base material 3 is working electrode, connects positive source; Wherein said positive source 5 is column roller,Described electrophoretic deposition system be also provided with the U-shaped groove structure symmetrical with positive source 5 to electrode 6,Connect power cathode.
Material recovery system, reclaims the electrophoresis liquid after electrophoretic deposition completes;
Electric-control system, connects the running of controlling electrophoretic deposition system.
Utilize above-mentioned electrophoretic deposition system to prepare the method for Silicon Based Anode Materials for Lithium-Ion Batteries, comprise as follows:
1) open electric-control system, drive the pulley on electrophoretic deposition pond, unreel copper foil base material as in tiselius apparatus;
2) open feeding system and make electrophoresis liquid enter electrophoretic deposition pond, wherein electrophoresis liquid is nano silicon material, carbonMaterial, cover carbon matrix precursor and dispersant be placed in decentralized medium dispersed become; Power-on, carries out electrophoresisDeposition obtains silico-carbo composite on copper foil base material; Powered-down, material recovery system recoveries electrophoresis liquid,Drive pulley rolling is the copper foil base material of depositing silicon-carbon composite, copper foil base material relative displacement, new Copper FoilBase material is moved in sedimentation basin;
3) open feeding system and make electrophoresis liquid enter electrophoretic deposition pond, repeat 2) operation, make a certain amount ofOn copper foil base material, all deposit and obtain silico-carbo composite;
4) silico-carbo composite is peeled off and is dried processing from copper foil base material, drier silico-carbo is multipleCondensation material is carbonization treatment in inert atmosphere, obtains lithium ion battery silico-carbo negative material.
Wherein, described nano silicon material comprises pure nano-silicon or nano silicon oxide, is preferably nano-silicon,Its diameter is 10-2000nm.
Wherein, described material with carbon element comprises CNT, carbon nano-fiber, nano carbon microsphere, Graphene or oxygenFunctionalized graphene, is preferably graphene oxide.
Wherein, described in, cover carbon matrix precursor for dissolving in decentralized medium and have one after high-temperature calcination in inert atmosphereDetermine the polymer of carbon residue, comprise glucose, polyoxyethylene, polyethylene glycol, polyvinyl alcohol, phenolic resins orAt least one in person's epoxy resin, is preferably polyethylene glycol.
Wherein, described decentralized medium is water, acetone, ethanol, acetylacetone,2,4-pentanedione, cyclohexane, isopropyl alcohol, vinegarAt least one in acid, carrene, methyl ethyl ketone or toluene; Described dispersant is citric acid, poly-Acetamide, polyacrylamide, ethyoxyl alkyl sodium sulphate, α-sodium olefin sulfonate, lauryl sodium sulfate,At least one in ethyoxyl alkyl ammonium sulfate or iodine.
Wherein, described inert atmosphere is at least one in nitrogen, argon gas or hydrogen; Described carbonization treatmentTemperature be 400-1000 DEG C, be preferably 700 DEG C; Time is 0.5-20h, is preferably 4h.
Adopt above technical scheme, design electrophoretic deposition system is volume to volume continued operation system, utilizes this to beSystem can be realized continuity prepared by Silicon Based Anode Materials for Lithium-Ion Batteries, and technological process is simple, mechanization journeySpend highly, be applicable to industrialized production in enormous quantities.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, not all at thisAny amendment of doing within bright spirit and principle, be equal to and replace and improvement etc., all should be included in the present inventionProtection domain within.
Claims (10)
1. an electrophoretic deposition system, is characterized in that, for volume to volume continous way operating system, comprises electrophoresisElectro-deposition system, the feeding system and the material recovery system that are connected with electrophoretic deposition system respectively, andElectric-control system, wherein
Feeding system, provides electrophoresis liquid;
Electrophoretic deposition system, comprises sedimentation basin, is provided with and unreels mouth and rolling mouth, institute on described sedimentation basinState and unreel mouthful and rolling mouth is provided with pulley, described pulley is used for transmitting copper foil base material, and described copper foil base material is workMake electrode, connect positive source;
Material recovery system, reclaims the electrophoresis liquid after electrophoretic deposition completes;
Electric-control system, connects the running of controlling electrophoretic deposition system.
2. a kind of electrophoretic deposition system according to claim 1, is characterized in that described electrophoretic depositionSystem is also provided with the square to electrode of two isolation symmetries, connects power cathode; Described mouth and the rolling mouth of unreelingPulley rotate drive copper foil base material by two square between electrode.
3. a kind of electrophoretic deposition system according to claim 1, is characterized in that described positive sourceFor column roller, described electrophoretic deposition system is also provided with the U-shaped groove structure symmetrical with positive sourceTo electrode, connect power cathode.
4. according to a kind of electrophoretic deposition system described in claim 1 or 3, it is characterized in that described copperPaper tinsel rolls connects and unreels mouthful and rolling mouth is provided with pulley, described pulley and post around the column roller of positive sourceThe rotation direction of shape roller is consistent, and drives the rotation of copper foil base material.
5. one kind is utilized the electrophoretic deposition system described in claim 1 to prepare Silicon Based Anode Materials for Lithium-Ion BatteriesMethod, it is characterized in that, comprise as follows:
1) open electric-control system, drive the pulley on electrophoretic deposition pond, unreel copper foil base material as in tiselius apparatus;
2) open feeding system and make electrophoresis liquid enter electrophoretic deposition pond, wherein electrophoresis liquid is nano silicon material, carbonMaterial, cover carbon matrix precursor and dispersant be placed in decentralized medium dispersed become; Power-on, carries out electrophoresisDeposition obtains silico-carbo composite on copper foil base material; Powered-down, material recovery system recoveries electrophoresis liquid,Drive pulley rolling is the copper foil base material of depositing silicon-carbon composite, copper foil base material relative displacement, new Copper FoilBase material is moved in sedimentation basin;
3) open feeding system and make electrophoresis liquid enter electrophoretic deposition pond, repeat 2) operation, make a certain amount ofOn copper foil base material, all deposit and obtain silico-carbo composite;
4) silico-carbo composite is peeled off and is dried processing from copper foil base material, drier silico-carbo is multipleCondensation material is carbonization treatment in inert atmosphere, obtains lithium ion battery silico-carbo negative material.
6. a kind of method of preparing Silicon Based Anode Materials for Lithium-Ion Batteries according to claim 5, its spyLevy and be, described nano silicon material comprises pure nano-silicon or nano silicon oxide, is preferably nano-silicon, itsDiameter is 10-2000nm.
7. a kind of method of preparing Silicon Based Anode Materials for Lithium-Ion Batteries according to claim 5, its spyLevy and be, described material with carbon element comprises CNT, carbon nano-fiber, nano carbon microsphere, Graphene or oxidationGraphene, is preferably graphene oxide.
8. a kind of method of preparing Silicon Based Anode Materials for Lithium-Ion Batteries according to claim 5, its spyLevy and be, described in cover carbon matrix precursor for dissolving in decentralized medium and having certain after high-temperature calcination in inert atmosphereThe polymer of carbon residue, comprise glucose, polyoxyethylene, polyethylene glycol, polyvinyl alcohol, phenolic resins orAt least one in epoxy resin, is preferably polyethylene glycol.
9. a kind of method of preparing Silicon Based Anode Materials for Lithium-Ion Batteries according to claim 5, its spyLevy and be, described decentralized medium be water, acetone, ethanol, acetylacetone,2,4-pentanedione, cyclohexane, isopropyl alcohol, acetic acid,At least one in carrene, methyl ethyl ketone or toluene; Described dispersant is citric acid, poly-acetylAmine, polyacrylamide, ethyoxyl alkyl sodium sulphate, α-sodium olefin sulfonate, lauryl sodium sulfate, ethoxyAt least one in base alkylsurfuric acid ammonium or iodine.
10. a kind of method of preparing Silicon Based Anode Materials for Lithium-Ion Batteries according to claim 5, itsBe characterised in that, described inert atmosphere is at least one in nitrogen, argon gas or hydrogen; Described carbonization treatmentTemperature be 400-1000 DEG C, be preferably 700 DEG C; Time is 0.5-20h, is preferably 4h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107022784A (en) * | 2016-02-02 | 2017-08-08 | 通用汽车环球科技运作有限责任公司 | Electrophoretic deposition for the electrode of lithium-base battery |
| CN112981499A (en) * | 2021-02-05 | 2021-06-18 | 太原科技大学 | Method and apparatus for electrodepositing active material particles on electrode current collector |
| US11430974B2 (en) | 2019-05-17 | 2022-08-30 | Ppg Industries Ohio, Inc. | System for roll-to-roll electrocoating of battery electrode coatings onto a foil substrate |
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| CN112981499A (en) * | 2021-02-05 | 2021-06-18 | 太原科技大学 | Method and apparatus for electrodepositing active material particles on electrode current collector |
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