CN109494374A - Lithium ion battery silicon-carbon cathode piece and preparation method thereof - Google Patents
Lithium ion battery silicon-carbon cathode piece and preparation method thereof Download PDFInfo
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- CN109494374A CN109494374A CN201811337217.6A CN201811337217A CN109494374A CN 109494374 A CN109494374 A CN 109494374A CN 201811337217 A CN201811337217 A CN 201811337217A CN 109494374 A CN109494374 A CN 109494374A
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- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 41
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 69
- 239000011248 coating agent Substances 0.000 claims abstract description 47
- 238000000576 coating method Methods 0.000 claims abstract description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011889 copper foil Substances 0.000 claims abstract description 36
- 239000011267 electrode slurry Substances 0.000 claims abstract description 14
- 239000007773 negative electrode material Substances 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 238000005520 cutting process Methods 0.000 claims abstract description 7
- 239000003575 carbonaceous material Substances 0.000 claims description 16
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 15
- 239000006258 conductive agent Substances 0.000 claims description 15
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 14
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 14
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 14
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 11
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims description 10
- 239000006245 Carbon black Super-P Substances 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- 239000005060 rubber Substances 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 2
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 claims 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011888 foil Substances 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 5
- 238000010410 dusting Methods 0.000 abstract description 4
- 239000011162 core material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011265 semifinished product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 241000784732 Lycaena phlaeas Species 0.000 description 2
- QZOVMCPHIQVUGV-UHFFFAOYSA-N [Si].[C].[Si] Chemical compound [Si].[C].[Si] QZOVMCPHIQVUGV-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- AQLLBJAXUCIJSR-UHFFFAOYSA-N OC(=O)C[Na] Chemical compound OC(=O)C[Na] AQLLBJAXUCIJSR-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Classifications
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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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- Engineering & Computer Science (AREA)
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- Manufacturing & Machinery (AREA)
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- Battery Electrode And Active Subsutance (AREA)
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Abstract
The invention discloses a kind of lithium ion battery silicon-carbon cathode pieces and preparation method thereof.The silicon-carbon cathode piece is in sandwich layer structure, is followed successively by netted micro through hole copper foil current collector, conductive carbon coating and negative electrode active material layer from inside to outside；Preparation method includes: 1) to prepare conductive carbon coating；2) conductive carbon coating is coated on its surface by the copper foil current collector for selecting netted micro through hole；3) negative electrode slurry is made；4) negative electrode slurry is coated in the netted micro through hole copper foil current collector with conductive carbon coating, obtains cathode pole piece through overbaking, roll-in, slitting, cross cutting.The present invention can form " I " fonts occlusive state by the material in copper foil gap and the material of micropore copper foil tow sides, improve the adhesion strength on foil surface, can effectively solving the problem of, silicon-carbon cathode piece thickens during dusting being dropped off because of pole piece caused by silicon substrate carbon negative pole material volume expansion and can also effectively slow down circulating battery after circulating battery.
Description
Technical field
The present invention relates to a kind of lithium ion battery silicon-carbon cathode pieces and preparation method thereof.
Background technique
With flourishing for China's new energy cause, lithium ion battery has become electric car at present and large-scale energy storage is set
Standby battery system is preferred.For new energy electric motor vehicle and energy storage base station to energy density, power density, security performance, use
High standard and high request in terms of service life and cost control surround lithium ion battery with high energy density core material and electrochemistry body
The research and development of system already become front end hot spot both domestic and external.The theoretical capacity of silicon materials is up to 4200mAh/g, deintercalate lithium ions
Current potential is low, platform electric discharge is steady and long, security performance is high, environmental-friendly pollution-free, these advantages close it greatly
Note, is presently believed to be in market the most preferred alternative materials of the carbon negative pole material of commercial applications prospect.Silicon-based anode material
Though expecting that theoretical capacity is high, platform is higher with respect to graphite to reduce analysis lithium, its conductivity is lower, causes electron transport rate low,
Volume expansion easily causes pole piece and drops off dusting after circulation.Volume expansion is big and the low battery polarization that will lead to of conductivity becomes larger, temperature
Degree increases, and influences the cycle performance and security performance of battery.
Patent 201610511702.5 discloses a kind of lithium ion battery negative electrode and preparation method thereof, the spy of preparation
Different nano inorganic layer, can make the caking property of silicon-carbon cathode active material layer and negative current collector more preferable, moreover it is possible in battery temperature mistake
Cause battery breaking when high.It both improves material by the way of silicon-carbon cathode material and the doping of the hollow carbon sphere of smaller particle
The compacted density of material, and improve the structural stability of cathode pole piece.In general, this is the electrical property and security performance of battery
Raising create good condition.But nano inorganic layer because of material itself the reason of, electric conductivity and caking property are lower,
Not can effectively solve silicon-carbon cathode still, bring electrical property deteriorates and safety problem due to volume expansion is big and conductivity is low, separately
Outside, the netted copper foil porosity used is excessive, will cause current collecting efficiency reduction, and be difficult to prevent from generating because of machining
Flash, these flashes be easy pierce through diaphragm cause battery short circuit.
Summary of the invention
The purpose of the present invention is overcoming the shortcomings of the prior art, a kind of electrical property that lithium battery can be improved and peace are provided
The silicon-carbon cathode piece of full performance.
It is a further object of the present invention to provide a kind of preparation methods of above-mentioned lithium ion battery silicon-carbon cathode piece.
In order to achieve the above object, lithium ion battery silicon-carbon cathode piece of the present invention be in sandwich layer structure, from inside to outside according to
Secondary is netted micro through hole copper foil current collector, conductive carbon coating and negative electrode active material layer；The conductive carbon coating with a thickness of
0.5~2 μm, negative electrode active material layer is with a thickness of 50~200 μm；Conductive carbon coating includes the conduction that mass ratio is 80~96%
Carbon, 1~5% sodium carboxymethylcellulose and 2~15% butadiene-styrene rubber, it is 50~70% that wherein conductive carbon, which includes mass ratio,
Carbon nanotube, 20~40% conductive carbon black and 5~20% graphene；Negative electrode active material include mass ratio be 95~
98% silicon carbon material, 0.5~1.5% conductive agent, 0.5~2.0% butadiene-styrene rubber and 0.2~1.5% carboxymethyl
Sodium cellulosate, wherein conductive agent includes the CNT for the Super-P and 65~75% that mass ratio is 25~35%.
Preferably, the netted micro through hole copper foil current collector with a thickness of 4~30 μm, porosity is 10~30%, hole
Diameter is 0.01~0.1mm.
Preferably, the mass ratio of silicon is 5~20% in the silicon carbon material.
1) preparation method of lithium ion battery silicon-carbon cathode piece of the present invention is the following steps are included: prepare conductive carbon coating: first
It is that 50~70% carbon nanotube, 20~40% conductive carbon black and 5~20% graphene are mixed into conduction by mass ratio
Then mass ratio is that 80~96% conductive carbon, 1~5% sodium carboxymethylcellulose and 2~15% butadiene-styrene rubber mix by carbon
Conductive carbon coating is uniformly made in conjunction；2) conductive carbon coating is coated on its surface, dried by the copper foil current collector for selecting netted micro through hole
Conductive carbon coating with a thickness of 0.5~2 μm after dry；3) by silicon carbon material, conductive agent, butadiene-styrene rubber: sodium carboxymethylcellulose with
Mass ratio is uniformly mixed for the ratio of 95~98:0.5~1.5:0.5~2.0:0.2~1.5, negative electrode slurry is made, wherein conductive agent
For the CNT for the Super-P and 65~75% that mass ratio is 25~35%；4) negative electrode slurry is coated in conductive carbon coating
In netted micro through hole copper foil current collector, cathode pole piece is obtained through overbaking, roll-in, slitting, cross cutting.
Preferably, the thickness for the netted micro through hole copper foil current collector that the step 2) is selected are as follows: 4~30 μm, porosity is
10~30%, aperture is 0.01~0.1mm.
Preferably, the mass ratio of silicon is 5~20% in silicon carbon material in step 3).
Preferably, baking condition described in step 4) is to keep the temperature 3 minutes at 120~140 DEG C.
By adopting the above technical scheme, negative current collector of the present invention carries out dual coating using netted micro through hole copper foil, relatively
It is coated in common copper foil, " I " fonts can be formed with the material of micropore copper foil tow sides by the material in copper foil gap and be engaged
State improves the adhesion strength on foil surface, can effectively solve after circulating battery because silicon substrate carbon negative pole material volume expansion causes
Pole piece the problem of dropping off dusting.In addition, the volume expansion of silicon substrate carbon negative pole material is spread during circulating battery after foil through-hole
Path can be converted into comprehensive migration, can effectively slow down the problem of silicon-carbon cathode piece during circulating battery thickens.In copper foil
Increase by one layer of special conductive carbon coating on collector, relative to common copper foil, negative current collector and negative electrode active material
Electric conductivity is greatly improved, and reduces the contact resistance of collector and active material.Further, organic conductive carbon coating is suitable
When the dosage for increasing negative electrode binder styrene butadiene rubber sbr, cathode formula and conductive carbon coating formula use specifications and models of the same race
Styrene butadiene rubber sbr, can be promoted between micropore copper foil and conductive carbon coating, the adhesion strength of conductive carbon coating and negative electrode slurry, into
One step reduces the impedance formed between any two by interface difference, improves the electrical property and security performance of battery.In addition, this hair
It is bright to use a kind of micropore copper foil as made from high-voltage arc or high power laser cheesing techniques, it is rushed relative to machinery is passed through at present
Netted copper foil made of hole, aperture is smaller, more evenly, and mechanical strength is bigger, and current collecting efficiency is higher, and does not generate flash,
Phenomena such as material leakage, roll banding and foil are broken, the processed negative electrode tab one being made are less prone in negative electrode slurry coating procedure
Cause property is more preferable, and electrical property is more preferably.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of one embodiment of the present invention.
Specific embodiment
The present invention will be further described below with reference to the drawings.
Embodiment 1:
As shown in Figure 1, lithium ion battery silicon-carbon cathode piece of the present invention is in sandwich layer structure, it is followed successively by from inside to outside netted
Micro through hole copper foil current collector 1, conductive carbon coating 2 and negative electrode active material layer 3；Pass through the material and micropore copper foil in copper foil gap 4
The material of tow sides can form " I " fonts occlusive state, improve the adhesion strength on foil surface, can effectively solve battery and follow
The problem of dropping off dusting because of pole piece caused by silicon substrate carbon negative pole material volume expansion after ring.In addition, after foil through-hole, circulating battery
Silicon substrate carbon negative pole material volume expansion diffusion path can be converted into comprehensive migration in the process, can effectively slow down circulating battery mistake
The problem of silicon-carbon cathode piece thickens in journey.
The preparation method of lithium ion battery silicon-carbon cathode piece of the present invention includes:
1) it prepares conductive carbon coating: being first 50% carbon nanotube, 40% conductive carbon black and 10% by mass ratio
Graphene is mixed into conductive carbon, then by mass ratio be 80% conductive carbon, 5% sodium carboxymethylcellulose and 15% butylbenzene
Conductive carbon coating is uniformly made in rubber mix；2) thickness is selected are as follows: 4 μm, porosity 10%, aperture is the netted micro- of 0.01mm
Conductive carbon coating is coated on its surface by through-hole copper foil current collector, conductive carbon coating with a thickness of 0.5 μm after drying；3) by silicon
Silicon carbon material that content is 5%, conductive agent, butadiene-styrene rubber: sodium carboxymethylcellulose is 95:1.5:2.0:1.5 ratio with mass ratio
Example is uniformly mixed, and negative electrode slurry is made, wherein conductive agent is the CNT for the Super-P and 75% that mass ratio is 25%；4) by cathode
Slurry is coated in the netted micro through hole copper foil current collector with conductive carbon coating, is obtained through overbaking, roll-in, slitting, cross cutting
Cathode pole piece.Wherein negative electrode active material coating surface density is 100g/m2, baking condition is to keep the temperature 3 minutes at 130 DEG C, compacting
Density is 1.50g/m3。
By positive plate, negative electrode tab, diaphragm pass through lamination, welding, encapsulation, be fabricated to semi-finished product battery core, be then injected into containing
Model thickness 7.5mm, width 90mm, length 190mm is made after chemical conversion, partial volume in the electrolyte of a small amount of VC and FEC
The battery of size, the nominal capacity of battery are 18Ah；Lithium ion battery obtained containing silicon carbon material negative electrode tab is at 25 DEG C
With the current discharge of 18Ah or 1C, initial discharge capacity 18.50Ah, 3C discharge capacity is 16.24Ah, the electric discharge times of 3C/1C
Rate is 87.78%, with the capacity retention ratio after 1C/1C charge-discharge cycle 1000 times for 86.19%.
Embodiment 2
The preparation method of lithium ion battery silicon-carbon cathode piece of the present invention includes:
1) it prepares conductive carbon coating: being first 70% carbon nanotube, 20% conductive carbon black and 10% by mass ratio
Graphene is mixed into conductive carbon, then by mass ratio be 96% conductive carbon, 1% sodium carboxymethylcellulose and 3% butylbenzene
Conductive carbon coating is uniformly made in rubber mix；2) thickness is selected are as follows: 30 μm, porosity 30%, aperture is the netted micro- of 0.1mm
Conductive carbon coating is coated on its surface by through-hole copper foil current collector, conductive carbon coating with a thickness of 2 μm after drying；3) silicon is contained
Silicon carbon material, the conductive agent, butadiene-styrene rubber that amount is 20%: sodium carboxymethylcellulose is that 98:0.5:0.5:1 ratio is mixed with mass ratio
It closes uniformly, negative electrode slurry is made, wherein conductive agent is the CNT for the Super-P and 65% that mass ratio is 35%；4) by negative electrode slurry
Coated in the netted micro through hole copper foil current collector with conductive carbon coating, cathode is obtained through overbaking, roll-in, slitting, cross cutting
Pole piece.Wherein negative electrode active material coating surface density is 95g/m2, baking condition is to keep the temperature 3 minutes, compacted density at 120 DEG C
For 1.40g/m3。
By positive plate, negative electrode tab, diaphragm pass through lamination, welding, encapsulation, be fabricated to semi-finished product battery core, be then injected into containing
Model thickness 7.5mm, width 90mm, length 190mm is made after chemical conversion, partial volume in the electrolyte of a small amount of VC and FEC
The battery of size, the nominal capacity of battery are 18Ah；Lithium ion battery obtained containing silicon carbon material negative electrode tab is at 25 DEG C
With the current discharge of 18Ah or 1C, initial discharge capacity 18.65Ah, 3C discharge capacity is 16.45Ah, the electric discharge times of 3C/1C
Rate is 88.20%, with the capacity retention ratio after 1C/1C charge-discharge cycle 1000 times for 86.43%.
Embodiment 3
The preparation method of lithium ion battery silicon-carbon cathode piece of the present invention includes:
1) it prepares conductive carbon coating: being first 60% carbon nanotube, 30% conductive carbon black and 10% by mass ratio
Graphene is mixed into conductive carbon, then by mass ratio be 93% conductive carbon, 5% sodium carboxymethylcellulose and 2% butylbenzene
Conductive carbon coating is uniformly made in rubber mix；2) thickness is selected are as follows: 16 μm, porosity 20%, aperture is the netted of 0.05mm
Conductive carbon coating is coated on its surface by micro through hole copper foil current collector, conductive carbon coating with a thickness of 1 μm after drying；3) by silicon
Silicon carbon material that content is 15%, conductive agent, butadiene-styrene rubber: sodium carboxymethylcellulose is 97:1:1.8:0.2 ratio with mass ratio
It is uniformly mixed, negative electrode slurry is made, wherein conductive agent is the CNT for the Super-P and 70% that mass ratio is 30%；4) cathode is starched
Material is coated in the netted micro through hole copper foil current collector with conductive carbon coating, is born through overbaking, roll-in, slitting, cross cutting
Pole pole piece.Wherein negative electrode active material coating surface density is 110g/m2, baking condition is to keep the temperature 3 minutes at 140 DEG C, is compacted close
Degree is 1.60g/m3。
By positive plate, negative electrode tab, diaphragm pass through lamination, welding, encapsulation, be fabricated to semi-finished product battery core, be then injected into containing
Model thickness 7.5mm, width 90mm, length 190mm is made after chemical conversion, partial volume in the electrolyte of a small amount of VC and FEC
The battery of size, the nominal capacity of battery are 18Ah；Lithium ion battery obtained containing silicon carbon material negative electrode tab is at 25 DEG C
With the current discharge of 18Ah or 1C, initial discharge capacity 18.58Ah, 3C discharge capacity is 16.36Ah, the electric discharge times of 3C/1C
Rate is 88.05%, with the capacity retention ratio after 1C/1C charge-discharge cycle 1000 times for 86.32%.
Embodiment 4
The preparation method of lithium ion battery silicon-carbon cathode piece of the present invention includes:
1) prepare conductive carbon coating: first by mass ratio be 65% carbon nanotube, 30% conductive carbon black and 5% stone
Black alkene is mixed into conductive carbon, then by mass ratio be 86% conductive carbon, 4% sodium carboxymethylcellulose and 10% butylbenzene rubber
Glue is uniformly mixed and conductive carbon coating is made；2) thickness is selected are as follows: 8 μm, porosity 25%, aperture is the netted micro- logical of 0.08mm
Conductive carbon coating is coated on its surface by hole copper foil current collector, conductive carbon coating with a thickness of 1.5 μm after drying；3) silicon is contained
Silicon carbon material, the conductive agent, butadiene-styrene rubber that amount is 10%: sodium carboxymethylcellulose is that 98:0.5:0.5:1 ratio is mixed with mass ratio
It closes uniformly, negative electrode slurry is made, wherein conductive agent is the CNT for the Super-P and 75% that mass ratio is 25%；4) by negative electrode slurry
Coated in the netted micro through hole copper foil current collector with conductive carbon coating, cathode is obtained through overbaking, roll-in, slitting, cross cutting
Pole piece.Wherein: it is 100g/m that negative electrode active material, which coats surface density,2, baking condition is 130 DEG C/3min, and compacted density is
1.50g/m3。
By positive plate, negative electrode tab, diaphragm pass through lamination, welding, encapsulation, be fabricated to semi-finished product battery core, be then injected into containing
Model thickness 7.5mm, width 90mm, length 190mm is made after chemical conversion, partial volume in the electrolyte of a small amount of VC and FEC
The battery of size, the nominal capacity of battery are 18Ah；Lithium ion battery obtained containing silicon carbon material negative electrode tab is at 25 DEG C
With the current discharge of 18Ah or 1C, initial discharge capacity 18.28Ah, 3C discharge capacity is 16.07Ah, the electric discharge times of 3C/1C
Rate is 87.91%, with the capacity retention ratio after 1C/1C charge-discharge cycle 1000 times for 86.27%.
Claims (7)
1. a kind of lithium ion battery silicon-carbon cathode piece, characterized in that lithium ion battery silicon-carbon cathode piece is in sandwich layer structure, by
It is followed successively by netted micro through hole copper foil current collector, conductive carbon coating and negative electrode active material layer from inside to outside；The conductive carbon coating
With a thickness of 0.5~2 μm, negative electrode active material layer is with a thickness of 50~200 μm；Conductive carbon coating includes that mass ratio is 80~96%
Conductive carbon, 1~5% sodium carboxymethylcellulose and 2~15% butadiene-styrene rubber, wherein conductive carbon include mass ratio be 50~
70% carbon nanotube, 20~40% conductive carbon black and 5~20% graphene；Negative electrode active material includes that mass ratio is
95~98% silicon carbon material, 0.5~1.5% conductive agent, 0.5~2.0% butadiene-styrene rubber and 0.2~1.5% carboxylic
Sodium carboxymethylcellulose pyce, wherein conductive agent includes the CNT for the Super-P and 65~75% that mass ratio is 25~35%.
2. lithium ion battery silicon-carbon cathode piece according to claim 1, characterized in that the netted micro through hole copper foil current collector
With a thickness of 4~30 μm, porosity is 10~30%, and aperture is 0.01~0.1mm.
3. according to claim 1 or 2 lithium ion battery silicon-carbon cathode piece, characterized in that silicon in the silicon carbon material
Mass ratio is 5~20%.
4. a kind of preparation method of lithium ion battery silicon-carbon cathode piece, characterized in that the following steps are included: 1) preparation conductive carbon applies
Layer: being first that 50~70% carbon nanotube, 20~40% conductive carbon black and 5~20% graphene are mixed by mass ratio
Conductive carbon, then by mass ratio be 80~96% conductive carbon, 1~5% sodium carboxymethylcellulose and 2~15% butylbenzene rubber
Glue is uniformly mixed and conductive carbon coating is made；2) conductive carbon coating is coated on its table by the copper foil current collector for selecting netted micro through hole
Face, conductive carbon coating with a thickness of 0.5~2 μm after drying；3) by silicon carbon material, conductive agent, butadiene-styrene rubber: carboxymethyl cellulose
Sodium is uniformly mixed with mass ratio for the ratio of 95~98:0.5~1.5:0.5~2.0:0.2~1.5, negative electrode slurry is made, wherein leading
Electric agent is the CNT of the Super-P that mass ratio is 25~35% and 65~75%；4) negative electrode slurry is coated in and is applied with conductive carbon
In the netted micro through hole copper foil current collector of layer, cathode pole piece is obtained through overbaking, roll-in, slitting, cross cutting.
5. the preparation method of lithium ion battery silicon-carbon cathode piece according to claim 4, characterized in that the step 2) was selected
The thickness of netted micro through hole copper foil current collector are as follows: 4~30 μm, porosity is 10~30%, and aperture is 0.01~0.1mm.
6. according to the preparation method of the lithium ion battery silicon-carbon cathode piece of claim 4 or 5, characterized in that silicon in step 3)
The mass ratio of silicon is 5~20% in carbon material.
7. according to the preparation method of the lithium ion battery silicon-carbon cathode piece of claim 4 or 5, characterized in that institute in step 4)
The baking condition stated is to keep the temperature 3 minutes at 120~140 DEG C.
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