CN109638223A - A kind of silicon-based anode of lithium ion battery and its preparation method and application - Google Patents
A kind of silicon-based anode of lithium ion battery and its preparation method and application Download PDFInfo
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- CN109638223A CN109638223A CN201811482674.4A CN201811482674A CN109638223A CN 109638223 A CN109638223 A CN 109638223A CN 201811482674 A CN201811482674 A CN 201811482674A CN 109638223 A CN109638223 A CN 109638223A
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- silicon
- based anode
- carbon
- lithium ion
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000010703 silicon Substances 0.000 title claims abstract description 35
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 85
- 238000000576 coating method Methods 0.000 claims abstract description 85
- 239000002002 slurry Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 239000011889 copper foil Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 12
- 239000004917 carbon fiber Substances 0.000 claims description 12
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 12
- 239000002041 carbon nanotube Substances 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000006258 conductive agent Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 239000011268 mixed slurry Substances 0.000 description 14
- 230000005611 electricity Effects 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 8
- 239000006245 Carbon black Super-P Substances 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000029052 metamorphosis Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011866 silicon-based anode active material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
-
- 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
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- 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
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to field of new energy technologies, more particularly to a kind of silicon-based anode and its preparation method and application of lithium ion battery, the silicon-based anode of lithium ion battery of the present invention, including collector, the collection liquid surface includes from inside to outside successively by coating carbon-coating, the coated material layer that conductive ink layer is formed, the form of coated material is threadiness, one or both of graininess, and coating material layers are formed by successively preparing two layers of slurry, alleviate volume expansion of silicon-based anode during charge and discharge cycles, overcome the bad disadvantage of silicon-based anode electric conductivity, to promote the high rate performance of battery.
Description
Technical field
The invention belongs to field of new energy technologies, and in particular to a kind of silicon-based anode of lithium ion battery and preparation method thereof
And application.
Background technique
With economic, humane, science and technology rapid development, interpersonal exchange is increasingly frequent, this is with regard to urgent need
Distance between shortening.Motor vehicle is as the main means of transport on land route, and quantity is in explosive growth, this huge
In convenient situation, it is necessarily accompanied with hidden danger.Most of motor vehicle is all to be run by fuel oil as power, is caused serious
Air pollution.And the protection of environment is theme instantly, to promote environmental quality, the energy of motor vehicle is from petroleum to cleaning energy
Source development, lithium ion battery because its specific capacity is big, cruising ability is strong, it is reusable due to receive an acclaim.
It is each that development high specific energy lithium ion battery needs to rely on the component parts such as anode, cathode, electrolyte and diaphragm
From performance and mutual cooperation.Cathode used in commercial Li-ion battery is based on graphite at present, and when charge and discharge, lithium ion exists
Graphite layers insertion abjection.Market its actual capacity of common graphite cathode is up to 360mAh/g or more, very close to it
Theoretical capacity.The theoretical capacity of silicon-based anode can reach 4212mAh/g, at this point, lithium forms Li in silicon4.4Si alloy, by
It is larger in meltage of the lithium in silicon, cause the volume change of the cathode during the charging process huge, it is swollen that highest can occur 420%
Swollen, the contraction of same volume can then occur for when electric discharge.Huge volume expansion and contraction cause silicon-based anode be easy to happen it is broken,
It falls off, is easy to lose effective electrical contact with collector in cyclic process, with the increase of charge and discharge number, be asked due to above-mentioned
The presence of topic causes to use silicon substrate poor as the lithium ion battery stability of cathode, and battery life is short.And silicon-based anode itself
Change have reached certain bottleneck, improve that there is also huge spaces in terms of collector.
For defect existing for current lithium ion battery silicium cathode, publication number 108511762A is by improving plus plate current-collecting body
Conductivity, promote the tensile strength of plus plate current-collecting body, reduce the thickness of plus plate current-collecting body, promote the volume of lithium ion battery
Energy density improves the low temperature charge-discharge performance of lithium battery.However the variation of this collector not can solve cell body product it is swollen
Swollen bring harm.
Summary of the invention
In view of the above problems, the present invention provides the silicon-based anode and its system of a kind of defect that can overcome silicon-based anode
Preparation Method and application.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of silicon-based anode of lithium ion battery, including collector, the collection liquid surface include from inside to outside successively by
Coat carbon-coating, the coated material layer that conductive ink layer is formed, the form of coated material is in threadiness, graininess
It is one or two kinds of.
Preferably, the basic material of the collector is copper foil.
Preferably, the conductive ink layer with a thickness of 0.2-1 μm.
Preferably, the raw material of the electrically conductive ink includes one or both of nano-Ag particles, nano-silver thread.
Further preferably, the partial size of the nano-Ag particles is 5-10nm, and the diameter of nano-silver thread is 10-20nm.
Preferably, the raw material of the coating carbon-coating includes the ingredient of following quality: carbon nanotube 1-5g, carbon fiber 1-
5g, conductive agent 15-35g, deionized water 45-60g, binder 5-9g, dispersing agent 5-8g.
Further preferably, it is described coating carbon-coating with a thickness of 1-5 μm.The thickness for controlling slurry, can not only reduce collector
Thickness, compress the volume of battery, can more promote the exchange rate between battery the two poles of the earth, improve the performance of battery.
The material of collector uses copper foil, and copper foil surface is relatively smooth, if directly contacting with silicon-based anode, the two is sticked
Attached power is inadequate, and active material is be easy to cause to fall off, and then reduces battery performance.And covering of the carbon-coating on copper foil is coated, it can be with
The roughening for greatly increasing copper foil surface can be promoted and be sticked when silicon-based anode is directly contacted with shaggy carbon coating
Power, while increasing the contact area of coating carbon-coating and collector, that is, exchange area of the silicon-based anode with collector is expanded, is dropped
Low interface contact resistance, the disadvantage for overcoming silicon-based anode electric conductivity bad.
Further preferably, the electrically conductive ink is by nano-Ag particles/nano-silver thread, propylene glycol monomethyl ether, dipropylene glycol first
Ether, ethyl alcohol are successively added in deionized water respectively, carry out high-speed stirred, then add acrylic resin, continue stirring and are formed
Uniform and stable mixture paste, last silk-screen (coating) is on coating carbon-coating.
Although collection liquid surface has had coating carbon-coating, amplitude of such coating carbon-coating to the performance boost of battery
Limited, one layer of electrically conductive ink of the further silk-screen of the present invention mainly passes through addition nano silver material, and change nano silver material
Form promote battery performance help, that is, further increase the conductive contact between collector and silicon-based anode, reduce interface electricity
Resistance, and adhesion strength between the two is improved, and nanometer silver coating itself has good flexibility, can further avoid pole piece
The bending folding being likely to occur in actual use declines or glues around the caused conductivity that falls off for the coat that may cause
Tie power decline.And the metamorphosis of the nano silver exactly in electrically conductive ink, promote the form of collection liquid surface coating material layers
Changed.
A kind of preparation method of the silicon-based anode of lithium ion battery, includes the following steps:
First carbon nanotube, carbon fiber, conductive agent, dispersing agent are successively added in deionized water, added again after being sufficiently stirred
Adding additives continue to stir, and form slurry after fully dispersed；
Slurry even application is formed into coating carbon-coating in copper foil surface, after being melted into, being dried, by electrically conductive ink silk
It is printed on coating carbon-coating and forms conductive ink layer, baking and curing obtains collector, is assembled into battery cathode.
The present invention enhances the performance of battery by improving collector, and the preparation process of collector is extremely simplified, required
Artificial and used time it is few, in chemical conversion, can by the temperature and time of control chemical conversion so that slurry mix obtain it is suitable
Softening degree, and binder therein is promoted to form effective cross-linked effect, stressed size is applied when being melted by control, is made
Pulp layer is combined closely with copper foil, slows down active material in battery and collector and conductive agent in long-term cyclic process
The defect for causing contact to be deteriorated due to volume expansion.Simultaneously because also having carried out conductive oil on the coating carbon-coating of copper foil surface
The silk-screen (coating) of ink is improving the conductive contact between collector and cathode, while reducing interface resistance, can further increase
The uptake of electrolyte promotes circulating battery stability.
Further preferably, the silicon-based anode of lithium ion battery is applied in lithium ion battery, the lithium ion battery
Silicon-based anode including lithium ion battery.
Compared with prior art, the present invention has the advantage that
(1) present invention improves the adhesive force of active material and collector using carbonaceous mixture is coated on copper foil, delays
Volume expansion of silicon-based anode during charge and discharge cycles is solved.
(2) present invention method that combines slurry coating with electrically conductive ink increases connecing for active material and collector
Contacting surface product, overcomes the bad disadvantage of silicon-based anode electric conductivity, to promote the high rate performance of battery.
(3) preparation method of collector of the present invention is succinctly effective, can greatly accelerate the commercialization process of silicon-based anode,
Facilitate the exploitation of high specific energy, the lithium ion battery of long-life.
Detailed description of the invention
Fig. 1 is the sectional view of collector of the present invention and its coated material layer.
In figure, 1, conductive ink layer；2, carbon-coating is coated；3, collector matrix.
Specific embodiment
The following is specific embodiments of the present invention, and technical scheme of the present invention will be further described, but the present invention is simultaneously
It is not limited to these embodiments.
Embodiment 1
It is weighed by the raw material of above-mentioned collector coating material, by 4.0g carbon nanotube, 4.0g carbon fiber, 30.0g is led
Electric carbon black Super P and 8.0g dispersing agent is successively added in 50.0g deionized water, is stirred 3h, then adds binder
6.0g continues to stir 30min, forms uniform and stable slurry；
Slurry is uniformly coated on the copper-foil conducting electricity of gauge thickness, forms carbon coating by rear dry out solvent is normalized into
Layer, the thickness of control coating carbon-coating is at 1.0 μm；
The nano-Ag particles for being 5nm by 1.0g partial size, 1.0g propylene glycol monomethyl ether, 1.0g dipropylene glycol methyl ether, 10.0g ethyl alcohol
Successively it is added in 20.0g deionized water, carries out high-speed stirred 2h, then adds 37% acrylic resin 30.0g, continue to stir
20min is mixed, uniform and stable mixed slurry is formed；
The surface of mixed slurry even spread to coating carbon-coating is formed into conductive ink layer, controls the thickness of conductive ink layer
At 0.4 μm, then dried to get collector is arrived for 120 DEG C.
Embodiment 2
It is weighed by the raw material of above-mentioned collector coating material, by 3.0g carbon nanotube, 3.0g carbon fiber, 20.0g is led
Electric carbon black Super P and 6.0g dispersing agent is successively added in 50.0g deionized water, is stirred 3h, then adds binder
6.0g continues to stir 30min, forms uniform and stable slurry；
Slurry is uniformly coated on the copper-foil conducting electricity of gauge thickness, forms carbon coating by rear dry out solvent is normalized into
Layer, the thickness of control coating carbon-coating is at 4.0 μm；
The nano-Ag particles for being 5nm by 1.0g partial size, 1.0g propylene glycol monomethyl ether, 1.0g dipropylene glycol methyl ether, 10.0g ethyl alcohol
Successively it is added in 20.0g deionized water, carries out high-speed stirred 2h, then adds 37% acrylic resin 30.0g, continue to stir
20min is mixed, uniform and stable mixed slurry is formed；
The surface of mixed slurry even spread to coating carbon-coating is formed into conductive ink layer, controls the thickness of conductive ink layer
At 0.2 μm, then dried to get collector is arrived for 120 DEG C.
Embodiment 3
It is weighed by the raw material of above-mentioned collector coating material, by 3.0g carbon nanotube, 3.0g carbon fiber, 20.0g is led
Electric carbon black Super P and 6.0g dispersing agent is successively added in 50.0g deionized water, is stirred 3h, then adds binder
6.0g continues to stir 30min, forms uniform and stable slurry；
Slurry is uniformly coated on certain thickness copper-foil conducting electricity, forms carbon coating by rear dry out solvent is normalized into
Layer, the thickness of control coating carbon-coating is at 2.0 μm；
The nano-Ag particles for being 10nm by 1.5g partial size, 1.0g propylene glycol monomethyl ether, 1.0g dipropylene glycol methyl ether, 10.0g second
Alcohol is successively added in 20.0g deionized water, carries out high-speed stirred 2h, then adds 37% acrylic resin 30.0g, continues
20min is stirred, uniform and stable mixed slurry is formed；
The surface of mixed slurry even spread to coating carbon-coating is formed into conductive ink layer, controls the thickness of conductive ink layer
At 1.0 μm, then dried to get collector is arrived for 120 DEG C.
Embodiment 4
It is weighed by the raw material of above-mentioned collector coating material, by 2.0g carbon nanotube, 3.0g carbon fiber, 20.0g is led
Electric carbon black Super P and 6.0g dispersing agent is successively added in 50.0g deionized water, is stirred 3h, then adds binder
8.0g continues to stir 30min, forms uniform and stable slurry；
Slurry is uniformly coated on certain thickness copper-foil conducting electricity, forms carbon coating by rear dry out solvent is normalized into
Layer, the thickness of control coating carbon-coating is at 3.0 μm；
It is 10 nanometers by 1.5g diameter, the nano-silver thread that draw ratio is 200,1.2g propylene glycol monomethyl ether, 1.5g dipropylene glycol
Methyl ether, 13.0g ethyl alcohol are successively added in 20.0g deionized water, carry out high-speed stirred 2h, then add 37% acrylic acid tree
Rouge 35.0g continues to stir 20min, forms uniform and stable mixed slurry；
The surface of mixed slurry even spread to coating carbon-coating is formed into conductive ink layer, controls the thickness of conductive ink layer
At 0.9 μm, then dried to get collector is arrived for 120 DEG C.
Embodiment 5
It is weighed by the raw material of above-mentioned collector coating material, by 2.0g carbon nanotube, 3.0g carbon fiber, 20.0g is led
Electric carbon black Super P and 6.0g dispersing agent is successively added in 50.0g deionized water, is stirred 3h, then adds binder
8.0g continues to stir 30min, forms uniform and stable slurry；
Slurry is uniformly coated on certain thickness copper-foil conducting electricity, forms carbon coating by rear dry out solvent is normalized into
Layer, the thickness of control coating carbon-coating is at 1.5 μm；
It is 20 nanometers by 1.0g diameter, the nano-silver thread that draw ratio is 100,1.5g propylene glycol monomethyl ether, 2.0g dipropylene glycol
Methyl ether, 15.0g ethyl alcohol are successively added in 25.0g deionized water respectively, carry out high-speed stirred 2h, then add 37% propylene
Acid resin 30.0g continues to stir 20min, forms uniform and stable mixed slurry；
The surface of mixed slurry even spread to coating carbon-coating is formed into conductive ink layer, controls the thickness of conductive ink layer
At 0.7 μm, then dried to get collector is arrived for 120 DEG C.
Embodiment 6
It is weighed by the raw material of above-mentioned collector coating material, by 4.0g carbon nanotube, 4.0g carbon fiber, 30.0g is led
Electric carbon black Super P and 8.0g dispersing agent is successively added in 55.0g deionized water, is stirred 3.0h, then addition bonding
Agent 8.0g continues to stir 30min, forms uniform and stable slurry；
Slurry is uniformly coated on certain thickness copper-foil conducting electricity, forms carbon coating by rear dry out solvent is normalized into
Layer, the thickness of control coating carbon-coating is at 1.3 μm；
It is 15 nanometers by 1.5g diameter, the nano-silver thread that draw ratio is 120,1.2g propylene glycol monomethyl ether, 1.5g dipropylene glycol
Methyl ether, 13.0g ethyl alcohol are successively added in 20.0g deionized water, carry out high-speed stirred 2h, then add 37% acrylic acid tree
Rouge 35.0g continues to stir 20min, forms uniform and stable mixed slurry；
The surface of mixed slurry even spread to coating carbon-coating is formed into conductive ink layer, controls the thickness of conductive ink layer
At 0.8 μm, then dried to get collector is arrived for 120 DEG C.
Embodiment 7
It is weighed by the raw material of above-mentioned collector coating material, by 2.0g carbon nanotube, 2.0g carbon fiber, 20.0g is led
Electric carbon black Super P and 6.0g dispersing agent is successively added in 55.0g deionized water, is stirred 3.0h, then addition bonding
Agent 6.0g continues to stir 30min, forms uniform and stable slurry；
Slurry is uniformly coated on certain thickness copper-foil conducting electricity, forms carbon coating by rear dry out solvent is normalized into
Layer, the thickness of control coating carbon-coating is at 1.0 μm；
The nano-Ag particles for being 15 nanometers by 2.0g diameter, 1.0g propylene glycol monomethyl ether, 1.0g dipropylene glycol methyl ether, 12.0g
Ethyl alcohol is successively added in 20.0g deionized water, carries out high-speed stirred 2h, then adds 37% acrylic resin 35.0g, after
Continuous stirring 20min, forms uniform and stable mixed slurry；
The surface of mixed slurry even spread to coating carbon-coating is formed into conductive ink layer, controls the thickness of conductive ink layer
At 0.8 μm, then dried to get collector is arrived for 120 DEG C.
Comparative example 1
It is weighed by the raw material of above-mentioned collector coating material, by 4.0g carbon nanotube, 4.0g carbon fiber, 30.0g is led
Electric carbon black Super P and 8.0g dispersing agent is successively added in 50.0g deionized water, is stirred 3h, then adds binder
6.0g continues to stir 30min, forms uniform and stable slurry；
Slurry is uniformly coated on certain thickness copper-foil conducting electricity, forms coat by rear dry out solvent is normalized into,
Control coat thickness 0.7 μm to get arrive collector.
Comparative example 2
It is weighed by the raw material of above-mentioned collector coating material, the nano silver for being 5nm by 1.0g partial size, 1.0g propylene glycol
Methyl ether, 1.0g dipropylene glycol methyl ether, 10.0g ethyl alcohol are successively added in 20.0g deionized water, carry out high-speed stirred 2h, then
The acrylic resin 30.0g of addition 37% continues to stir 20min, forms uniform and stable slurry；
Slurry is uniformly coated on certain thickness copper-foil conducting electricity, forms coat by rear dry out solvent is normalized into,
The thickness of coat is controlled at 0.15 μm, is then dried to get collector is arrived for 120 DEG C.
Comparative example 3
Negative current collector directlys adopt conventional surface and does not have any addition or specially treated without any processing
Commercially available copper foil.
Embodiment 1-7 and comparative example the 1-3 collector obtained are applied in battery by the present invention, wherein the anode of battery,
Cathode preparation is as follows:
Anode preparation:
By positive active material, conductive agent, binder and solvent NMP, 90:5:5:100 is mixed in agate pot according to the proportion
In, it is placed in planetary ball mill and is stirred 4h and obtains anode sizing agent, anode sizing agent is coated on carbon-coated aluminum foils collection with coating machine
On fluid, vacuum drying volatilization PEG, then the electrode of coating is dried in vacuo to obtain lithium ion cell positive after winding up roller pressure, cutting
Piece.
Cathode preparation:
Negative electrode active material, cathode conductive agent, negative electrode binder and cathode solvent are mixed evenly, cathode slurry is made
Negative electrode slurry is coated on the special negative current collector of the present invention, negative electrode tab is made by material.
Battery assembly: positive plate, diaphragm and negative electrode tab are fitted into battery case, and battery core seals to obtain lithium after injecting electrolyte
Ion battery.
Battery after embodiment 1-7 and comparative example 1-3 assembly is tested, its pole piece peeling force, pole piece conductance are tested
Rate, cathode, specific energy, the results are shown in Table 1:
Table 1: the performance of battery in embodiment 1-7 and comparative example 1-3
From the point of view of data in table, embodiment 1-7 uses the method for the present invention, and the peeling force of negative electrode tab gets a promotion, explanation
The degree of sticking of cathode on a current collector increases；The resistance and battery ohmic internal resistance for comparing negative electrode tab can see, embodiment 1-7
After the method for the present invention, cathode resistance is substantially reduced, and the ohmic internal resistance of battery is also greatly lowered, and illustrates negative current collector
After the method for the present invention is handled, the interface resistance between silicon-based anode active material and collector is greatly lowered；Electricity simultaneously
The first charge discharge efficiency in pond gets a promotion, and the cycle life of battery is improved significantly.
It is skilled to this field although present invention has been described in detail and some specific embodiments have been cited
For technical staff, as long as it is obvious for can making various changes or correct without departing from the spirit and scope of the present invention.
Claims (8)
1. a kind of silicon-based anode of lithium ion battery, including collector, which is characterized in that the collection liquid surface include from it is interior to
The coated material layer that is successively formed by coating carbon-coating, conductive ink layer outside, the form of coated material be it is fibrous,
It is one or both of granular.
2. silicon-based anode according to claim 1, which is characterized in that the conductive ink layer with a thickness of 0.2-1 μm.
3. silicon-based anode according to claim 1 or 2, which is characterized in that the raw material of the electrically conductive ink includes nano silver
One or both of particle, nano-silver thread.
4. silicon-based anode according to claim 3, which is characterized in that the partial size of the nano-Ag particles is 5-10nm, is received
The diameter of rice silver wire is 10-20nm.
5. silicon-based anode according to claim 1, which is characterized in that the raw material of the coating carbon-coating includes following quality
Ingredient: carbon nanotube 1-5g, carbon fiber 1-5g, conductive agent 15-35g, deionized water 45-60g, binder 5-9g, dispersing agent 5-
8g。
6. preparation method according to claim 1 or 5, which is characterized in that it is described coating carbon-coating with a thickness of 1-5 μm.
7. a kind of preparation method of the silicon-based anode of lithium ion battery as described in claim 1, which is characterized in that the method
Include the following steps:
First carbon nanotube, carbon fiber, conductive agent, dispersing agent are successively added in deionized water, added again after being sufficiently stirred viscous
Agent is tied, continues to stir, forms slurry after fully dispersed；
By slurry even application in copper foil surface formed coating carbon-coating, after being melted into, being dried, by electrically conductive ink silk-screen in
Conductive ink layer is formed on coating carbon-coating, baking and curing obtains collector, is assembled into battery cathode.
8. a kind of application of silicon-based anode of lithium ion battery as described in claim 1 in lithium ion battery, feature exist
In the lithium ion battery includes the silicon-based anode of lithium ion battery.
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| CN110085806A (en) * | 2019-04-30 | 2019-08-02 | 湖北锂诺新能源科技有限公司 | Silicon-carbon cathode and preparation method thereof and lithium ion battery |
| CN113193161A (en) * | 2021-04-28 | 2021-07-30 | 珠海冠宇电池股份有限公司 | Electrode assembly and electrochemical device |
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| CN106299247A (en) * | 2016-09-26 | 2017-01-04 | 深圳市卓能新能源股份有限公司 | A kind of lithium ion battery aqueous silicon-base negative plate and preparation method thereof |
| CN106797033A (en) * | 2014-08-25 | 2017-05-31 | 日产自动车株式会社 | Electric connection structure |
| CN107528044A (en) * | 2017-07-25 | 2017-12-29 | 深圳市沃特玛电池有限公司 | A kind of lithium ion battery negative electrode and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106797033A (en) * | 2014-08-25 | 2017-05-31 | 日产自动车株式会社 | Electric connection structure |
| CN106299247A (en) * | 2016-09-26 | 2017-01-04 | 深圳市卓能新能源股份有限公司 | A kind of lithium ion battery aqueous silicon-base negative plate and preparation method thereof |
| CN107528044A (en) * | 2017-07-25 | 2017-12-29 | 深圳市沃特玛电池有限公司 | A kind of lithium ion battery negative electrode and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110085806A (en) * | 2019-04-30 | 2019-08-02 | 湖北锂诺新能源科技有限公司 | Silicon-carbon cathode and preparation method thereof and lithium ion battery |
| CN113193161A (en) * | 2021-04-28 | 2021-07-30 | 珠海冠宇电池股份有限公司 | Electrode assembly and electrochemical device |
| CN113193161B (en) * | 2021-04-28 | 2024-04-09 | 珠海冠宇电池股份有限公司 | Electrode assembly and electrochemical device |
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