CN110444746A - A kind of silicon-carbon cathode slurry, preparation method, cathode pole piece and lithium ion battery - Google Patents
A kind of silicon-carbon cathode slurry, preparation method, cathode pole piece and lithium ion battery Download PDFInfo
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- CN110444746A CN110444746A CN201910676534.9A CN201910676534A CN110444746A CN 110444746 A CN110444746 A CN 110444746A CN 201910676534 A CN201910676534 A CN 201910676534A CN 110444746 A CN110444746 A CN 110444746A
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- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000006257 cathode slurry Substances 0.000 title claims abstract description 62
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000010406 cathode material Substances 0.000 claims abstract description 31
- 239000006258 conductive agent Substances 0.000 claims abstract description 21
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000002562 thickening agent Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 39
- 239000011889 copper foil Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 18
- 238000005520 cutting process Methods 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 238000004513 sizing Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000005030 aluminium foil Substances 0.000 claims description 8
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical group C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 238000010030 laminating Methods 0.000 claims description 8
- 238000003475 lamination Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 8
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003466 welding Methods 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims 1
- -1 polypropylene Polymers 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 11
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000006378 damage Effects 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 230000006798 recombination Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002232 CNT15 Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000008961 swelling Effects 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
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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 & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of silicon-carbon cathode slurry, preparation method, cathode pole piece and lithium ion batteries, silicon-carbon cathode slurry weight percent component raw material includes: silicon-carbon cathode material 90.5-97.4%, conductive agent 0.6-3.5%, thickener 1.0-3.0%, binder 1.0-3.0%；The conductive agent includes multi wall CNT and single wall CNT.The silicon-carbon cathode slurry conductive agent compound by using single wall CNT and multi wall CNT, outstanding electric conductivity can be provided, silicon-carbon cathode particle can also be held onto, inhibit the expansion of cathode particle, silicon-carbon cathode slurry is applied in cathode pole piece, negative terminal surface is reduced due to SEI film destruction recombination and powder of detached caused by expanding repeatedly, to promote the cycle performance of silicon carbon material；Multi wall CNT and single wall CNT are wrapped in cathode particle surface jointly, will not be detached from due to the expansion repeatedly of cathode with cathode particle and electric conductivity is made to be deteriorated, this has been further ensured that the stability of circulation.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of silicon-carbon cathode slurry, preparation method, cathode poles
Piece and lithium ion battery.
Background technique
With output voltage is high, energy density is big, self discharge is small, memory-less effect, good cycle, operating temperature range
Width and it is environmentally friendly the advantages that lithium ion battery, be widely used to portable electronic product and consumer electronics and produce
In product, and in recent years along with the development of electric car and its technology is able to fast development.
But the lithium ion battery of high-energy density is only the direction of future development, and the promotion of energy density is mainly wrapped
Include two approach:
First, under current material system, increases the compacted density of positive and negative pole material, using less electrolyte and uses
Thinner auxiliary material is to promote volume energy density and mass energy density, however the excessive performance that will affect material of compacted density,
The use for reducing electrolyte will lead to the decline of cycle performance, and not only increase manufacturing process difficulty using thinner auxiliary material,
It also will increase security risk simultaneously；
Second, the specific capacity or the exploitation higher novel positive and negative pole material of energy density of existing positive and negative pole material are promoted, is passed
The negative electrode material of system mainly includes graphite carbon material, although such material has a clear superiority in cost, technique and performance,
It is the demand for development for being unable to satisfy high-energy density battery core, high-capacity cathode material novel at present mainly includes silicon-carbon, silicon
Oxygen, metal and its oxide etc., wherein the theoretical specific capacity of silicium cathode has reached 4200mAh/g, much higher than the theoretical ratio of graphite
Capacity 375mAh/g, and battery manufacturer, Japan and Korea S is by silicon-carbon cathode application.
At present, for domestic silicon-carbon cathode almost without business application is obtained, main problem is that low electron conduction is poor
And the problems such as cyclic process huge volume expansion, cause the circulation of battery core to decay rapidly, while causing battery core thickness swelling tight
Weight, security performance are severely impacted.It is existing poor for silicon-carbon cathode relative electrical conductivity, typically use ion doping and carbon
The method of cladding promotes electron conduction, but these schemes are improved from the nanosizing and Composite of material, not only
The difficulty and complexity of material technology are improved, but also add somewhat to the cost of material.
Summary of the invention
In view of this, the present invention provides a kind of silicon-carbon cathode slurry, preparation method, cathode pole piece and lithium ion battery,
This silicon-carbon cathode slurry is applied to cathode pole piece, and the expansion rate of silicon-carbon cathode pole piece can be significantly reduced, promote lithium ion battery
Cycle performance and energy density.
A kind of silicon-carbon cathode slurry, weight percent component raw material include:
The conductive agent includes multi wall CNT and single wall CNT.
Preferably, the active material silicon in the silicon-carbon cathode material is monomer silicon, silica and aoxidizes in sub- silicon
It is one or more；Active material carbon in the silicon-carbon cathode material is natural graphite, artificial graphite, composite graphite, soft carbon, hard
One of carbon and carbonaceous mesophase spherules are a variety of.
Preferably, the mass ratio of the multi wall CNT and single wall CNT is 1-30.
Preferably, the single wall CNT length is 5 μm -20 μm；The multi wall CNT length is 2 μm -5 μm.
Preferably, the thickener is sodium carboxymethylcellulose.
Preferably, the binder is at least one of butadiene-styrene rubber, polyacrylic acid, polyvinyl alcohol and sodium alginate.
A kind of preparation method of silicon-carbon cathode slurry, method include:
Stirred tank is added with water in thickener to mix, stirred tank rotation revolving speed is 1500-2500rpm, and revolution revolving speed is 25-
35rpm stirs 180-240min, obtains mixture a；
Multi wall CNT and single wall CNT is added in mixture a and is mixed, stirred tank rotation revolving speed is 1500-2500rpm, public
Speed of walking around is 25-35rpm, stirs 120-150min, obtains mixture b；
Stirring in mixture b, which is added, in the silicon-carbon cathode material of half soaks it sufficiently, and rotation revolving speed is 500-
1000rpm, revolution revolving speed are that 10-15rpm is added the other half silicon-carbon cathode material and is stirred after stirring 5-10min, are stirred
Kettle rotation revolving speed is 2000-3000rpm, and revolution revolving speed is 30-40rpm, stirs 200-300min, obtains mixture c；
Binder is added in mixture c, stirred tank rotation revolving speed is 1500-2000rpm, and revolution revolving speed is 25-
35rpm stirs 60-120min, obtains the silicon-carbon cathode slurry that viscosity is 2000-4000mPas.
A kind of cathode pole piece, including porous copper foil and above-mentioned silicon-carbon cathode slurry, the silicon-carbon cathode slurry is uniform
Coated in porous copper foil surface, cathode pole piece is obtained after drying, roll-in, cross cutting.
Preferably, the porous copper foil is with a thickness of 6-20 μm, porosity 5-30%；The two-sided face of the cathode pole piece is close
Degree is 150-250g/m2；The compacted density of the cathode pole piece is 1.2-1.7g/cc.
A kind of lithium ion battery, including anode pole piece, diaphragm, electrolyte and above-mentioned cathode pole piece, the anode pole
Piece, cathode pole piece collocation diaphragm obtain naked battery core by laminating machine lamination, and welding electrode ear, sealing, injection electrolyte, chemical conversion obtain
Lithium ion battery；
The anode pole piece the preparation method comprises the following steps:
Positive electrode, binder, conductive agent and N-Methyl pyrrolidone are mixed, anode sizing agent is obtained, it will be positive
Slurry is coated on aluminium foil using coating machine, and uniform coating, drying, roll-in, cross cutting obtain anode pole piece；
The positive electrode includes one of cobalt acid lithium, nickle cobalt lithium manganate, nickel cobalt lithium aluminate.
The present invention provides a kind of silicon-carbon cathode slurry, preparation method, cathode pole piece and lithium ion battery, silicon-carbon cathode slurries
Expect the conductive agent compound by using single wall CNT and multi wall CNT, special line dotted line conductive network can not only provide outstanding
Electric conductivity, moreover it is possible to hold onto silicon-carbon cathode particle, inhibit the expansion of cathode particle, silicon-carbon cathode slurry is applied in cathode pole piece
When, negative terminal surface is reduced due to SEI film destruction recombination and powder of detached caused by expanding repeatedly, to promote following for silicon carbon material
Ring performance；Multi wall CNT and single wall CNT are wrapped in cathode particle surface jointly, will not due to the expansion repeatedly of cathode with cathode
Grain is detached from and electric conductivity is made to be deteriorated, this has been further ensured that the stability of circulation；Cathode pole piece can be given swollen using porous copper foil
The certain spatial cache of swollen graphite can equally can be reduced the expansion rate of cathode pole piece, while lighter quality energy to a certain degree
It is significant that the mass energy density of battery core is provided.
Detailed description of the invention
Technical solution in order to illustrate the embodiments of the present invention more clearly, below will be to needed in embodiment description
Attached drawing is briefly described, it should be apparent that, the Characterization result figure that drawings in the following description are some embodiments of the invention,
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings
Other attached drawings.
Fig. 1 is cathode pole piece manufacturing process schematic diagram.
Appended drawing reference
11 hole, 12 copper foil
13 silicon-carbon cathode slurry, 14 multi wall CNT
15 single wall CNT, 16 porous copper foil
17 binder, 18 silicon-carbon cathode material
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are some of the embodiments of the present invention, instead of all the embodiments.Based on the implementation in the present invention
Example, every other embodiment obtained by those of ordinary skill in the art without making creative efforts belong to
The scope of protection of the invention.
It should be appreciated that ought use in this specification and in the appended claims, term " includes " and "comprising" instruction
Described feature, entirety, step, operation, the presence of element and/or component, but one or more of the other feature, whole is not precluded
Body, step, operation, the presence or addition of element, component and/or its set.
It will be further appreciated that the term "and/or" used in description of the invention and the appended claims is
Refer to any combination and all possible combinations of one or more of associated item listed, and including these combinations.
A kind of silicon-carbon cathode slurry, weight percent component raw material include:
Wherein, it is 1-30, single wall that conductive agent, which includes the mass ratio of multi wall CNT and single wall CNT, multi wall CNT and single wall CNT,
CNT length is 5 μm -20 μm；Multi wall CNT length is 2 μm -5 μm；Active material silicon in silicon-carbon cathode material is monomer silicon, oxygen
One of SiClx and the sub- silicon of oxidation are a variety of；Active material carbon in silicon-carbon cathode material be natural graphite, artificial graphite,
One of composite graphite, soft carbon, hard carbon and carbonaceous mesophase spherules are a variety of；Thickener is sodium carboxymethylcellulose (CMC)；
Binder is at least one of butadiene-styrene rubber (SBR), polyacrylic acid, polyvinyl alcohol and sodium alginate.
A kind of preparation method of silicon-carbon cathode slurry, method include:
Stirred tank is added with water in thickener to mix, stirred tank rotation revolving speed is 1500-2500rpm, and revolution revolving speed is 25-
35rpm stirs 180-240min, obtains mixture a；
Multi wall CNT and single wall CNT is added in mixture a and is mixed, stirred tank rotation revolving speed is 1500-2500rpm, public
Speed of walking around is 25-35rpm, stirs 120-150min, obtains mixture b；
Stirring in mixture b, which is added, in the silicon-carbon cathode material of half soaks it sufficiently, and rotation revolving speed is 500-
1000rpm, revolution revolving speed are that 10-15rpm is added the other half silicon-carbon cathode material and is stirred after stirring 5-10min, are stirred
Kettle rotation revolving speed is 2000-3000rpm, and revolution revolving speed is 30-40rpm, stirs 200-300min, obtains mixture c；
Binder is added in mixture c, stirred tank rotation revolving speed is 1500-2000rpm, and revolution revolving speed is 25-
35rpm stirs 60-120min, obtains the silicon-carbon cathode slurry that viscosity is 2000-4000mPas.
A kind of cathode pole piece, including porous copper foil and above-mentioned silicon-carbon cathode slurry, the silicon-carbon cathode slurry is uniform
Coated in porous copper foil surface, cathode pole piece is obtained after drying, roll-in, cross cutting.
Wherein, porous copper foil is with a thickness of 6-20 μm, porosity 5-30%；The two-sided surface density of cathode pole piece is 150-
250g/m2；The compacted density of cathode pole piece is 1.2-1.7g/cc.
A kind of lithium ion battery, including anode pole piece, diaphragm, electrolyte and above-mentioned cathode pole piece, the anode pole
Piece, cathode pole piece collocation diaphragm obtain naked battery core by laminating machine lamination, and welding electrode ear, sealing, injection electrolyte, chemical conversion obtain
Lithium ion battery；
Anode pole piece the preparation method comprises the following steps: positive electrode, binder, conductive agent and NMP are mixed, obtain positive slurry
Material, anode sizing agent is coated on aluminium foil using coating machine, and uniform coating, drying, roll-in, cross cutting obtain anode pole piece；Its
In, positive electrode includes one of cobalt acid lithium, nickle cobalt lithium manganate, nickel cobalt lithium aluminate.
Specific embodiment 1
A kind of silicon-carbon cathode slurry, weight percent component raw material include:
A kind of preparation method of silicon-carbon cathode slurry, method include:
Stirred tank is added with water in sodium carboxymethylcellulose to mix, stirred tank rotation revolving speed is 1500rpm, and revolution revolving speed is
35rpm stirs 240min, obtains mixture a；
Multi wall CNT and single wall CNT is added in mixture a and is mixed, stirred tank rotation revolving speed is 2500rpm, and revolution turns
Speed is 25rpm, stirs 150min, obtains mixture b；
Stirring in mixture b, which is added, in the silicon-carbon cathode material of half soaks it sufficiently, and rotation revolving speed is 500rpm, public
Speed of walking around is that 15rpm is added the other half silicon-carbon cathode material and is stirred, stirred tank rotation revolving speed is after stirring 5min
3000rpm, revolution revolving speed are 30rpm, stir 300min, obtain mixture c；
Butadiene-styrene rubber is added in mixture c, stirred tank rotation revolving speed is 1500rpm, and revolution revolving speed is 35rpm, stirring
60min obtains the silicon-carbon cathode slurry that viscosity is 4000mPas.
A kind of cathode pole piece, including porous copper foil and above-mentioned silicon-carbon cathode slurry, the silicon-carbon cathode slurry is uniform
Coated in porous copper foil surface, cathode pole piece is obtained after drying, roll-in, cross cutting.
Wherein, porous copper foil is with a thickness of 8 μm, porosity 15%；The two-sided surface density of cathode pole piece is 200g/m2；It is negative
The compacted density of pole pole piece is 1.6g/cc.
A kind of lithium ion battery, including anode pole piece, diaphragm, electrolyte and above-mentioned cathode pole piece, anode pole piece is born
Pole piece collocation diaphragm in pole obtains naked battery core by laminating machine lamination, and welding electrode ear, sealing, injection electrolyte, chemical conversion obtain lithium ion
Battery；
Wherein, anode pole piece the preparation method comprises the following steps: by lithium cobaltate cathode material, binder, conductive agent and N- methylpyrrole
Alkanone is mixed, and anode sizing agent is obtained, and anode sizing agent is coated on aluminium foil using coating machine, uniformly coating, drying, roller
Pressure, cross cutting, obtain anode pole piece.
Specific embodiment 2
A kind of silicon-carbon cathode slurry, weight percent component raw material include:
A kind of preparation method of silicon-carbon cathode slurry, method include:
Stirred tank is added with water in sodium carboxymethylcellulose to mix, stirred tank rotation revolving speed is 2500rpm, and revolution revolving speed is
25rpm stirs 180min, obtains mixture a；
Multi wall CNT and single wall CNT is added in mixture a and is mixed, stirred tank rotation revolving speed is 1500rpm, and revolution turns
Speed is 35rpm, stirs 120min, obtains mixture b；
Stirring in mixture b, which is added, in the silicon-carbon cathode material of half soaks it sufficiently, and rotation revolving speed is 1000rpm,
Revolution revolving speed is that 10rpm is added the other half silicon-carbon cathode material and is stirred, stirred tank rotation revolving speed is after stirring 10min
2000rpm, revolution revolving speed are 40rpm, stir 200min, obtain mixture c；
Butadiene-styrene rubber is added in mixture c, stirred tank rotation revolving speed is 2000rpm, and revolution revolving speed is 25rpm, stirring
120min obtains the silicon-carbon cathode slurry that viscosity is 3000mPas.
A kind of cathode pole piece, including porous copper foil and above-mentioned silicon-carbon cathode slurry, the silicon-carbon cathode slurry is uniform
Coated in porous copper foil surface, cathode pole piece is obtained after drying, roll-in, cross cutting.
Wherein, porous copper foil is with a thickness of 8 μm, porosity 15%；The two-sided surface density of cathode pole piece is 200g/m2；It is negative
The compacted density of pole pole piece is 1.6g/cc.
A kind of lithium ion battery, including anode pole piece, diaphragm, electrolyte and above-mentioned cathode pole piece, anode pole piece is born
Pole piece collocation diaphragm in pole obtains naked battery core by laminating machine lamination, and welding electrode ear, sealing, injection electrolyte, chemical conversion obtain lithium ion
Battery；
Wherein, anode pole piece the preparation method comprises the following steps: by nickel-cobalt lithium manganate cathode material, binder, conductive agent and N- methyl
Pyrrolidones is mixed, and anode sizing agent is obtained, and anode sizing agent is coated on aluminium foil using coating machine, uniformly coat, dry,
Roll-in, cross cutting, obtain anode pole piece.
Specific embodiment 3
A kind of silicon-carbon cathode slurry, weight percent component raw material include:
A kind of preparation method of silicon-carbon cathode slurry, method include:
Stirred tank is added with water in sodium carboxymethylcellulose to mix, stirred tank rotation revolving speed is 1800rpm, and revolution revolving speed is
27rpm stirs 190min, obtains mixture a；
Multi wall CNT and single wall CNT is added in mixture a and is mixed, stirred tank rotation revolving speed is 1900rpm, and revolution turns
Speed is 28rpm, stirs 130min, obtains mixture b；
Stirring in mixture b, which is added, in the silicon-carbon cathode material of half soaks it sufficiently, and rotation revolving speed is 800rpm, public
Speed of walking around is that 12rpm is added the other half silicon-carbon cathode material and is stirred, stirred tank rotation revolving speed is after stirring 7min
2500rpm, revolution revolving speed are 32rpm, stir 230min, obtain mixture c；
Butadiene-styrene rubber is added in mixture c, stirred tank rotation revolving speed is 1700rpm, and revolution revolving speed is 28rpm, stirring
90min obtains the silicon-carbon cathode slurry that viscosity is 2000mPas.
A kind of cathode pole piece, including porous copper foil and above-mentioned silicon-carbon cathode slurry, the silicon-carbon cathode slurry is uniform
Coated in porous copper foil surface, cathode pole piece is obtained after drying, roll-in, cross cutting.
Wherein, porous copper foil is with a thickness of 8 μm, porosity 15%；The two-sided surface density of cathode pole piece is 200g/m2；It is negative
The compacted density of pole pole piece is 1.6g/cc.
A kind of lithium ion battery, including anode pole piece, diaphragm, electrolyte and above-mentioned cathode pole piece, anode pole piece is born
Pole piece collocation diaphragm in pole obtains naked battery core by laminating machine lamination, and welding electrode ear, sealing, injection electrolyte, chemical conversion obtain lithium ion
Battery；
Wherein, anode pole piece the preparation method comprises the following steps: by nickel cobalt lithium aluminate cathode material, binder, conductive agent and N- methyl
Pyrrolidones is mixed, and anode sizing agent is obtained, and anode sizing agent is coated on aluminium foil using coating machine, uniformly coat, dry,
Roll-in, cross cutting, obtain anode pole piece.
Specific embodiment 4
A kind of silicon-carbon cathode slurry, weight percent component raw material include:
A kind of preparation method of silicon-carbon cathode slurry, method include:
Stirred tank is added with water in sodium carboxymethylcellulose to mix, stirred tank rotation revolving speed is 2200rpm, and revolution revolving speed is
32rpm stirs 210min, obtains mixture a；
Multi wall CNT and single wall CNT is added in mixture a and is mixed, stirred tank rotation revolving speed is 1900rpm, and revolution turns
Speed is 29rpm, stirs 140min, obtains mixture b；
Stirring in mixture b, which is added, in the silicon-carbon cathode material of half soaks it sufficiently, and rotation revolving speed is 600rpm, public
Speed of walking around is that 14rpm is added the other half silicon-carbon cathode material and is stirred, stirred tank rotation revolving speed is after stirring 9min
2300rpm, revolution revolving speed are 38rpm, stir 280min, obtain mixture c；
Butadiene-styrene rubber is added in mixture c, stirred tank rotation revolving speed is 1800rpm, and revolution revolving speed is 29rpm, stirring
90min obtains the silicon-carbon cathode slurry that viscosity is 2800mPas.
A kind of cathode pole piece, including porous copper foil and above-mentioned silicon-carbon cathode slurry, the silicon-carbon cathode slurry is uniform
Coated in porous copper foil surface, cathode pole piece is obtained after drying, roll-in, cross cutting.
Wherein, porous copper foil is with a thickness of 6 μm, porosity 5%；The two-sided surface density of cathode pole piece is 250g/m2；Cathode
The compacted density of pole piece is 1.7g/cc.
A kind of lithium ion battery, including anode pole piece, diaphragm, electrolyte and above-mentioned cathode pole piece, anode pole piece is born
Pole piece collocation diaphragm in pole obtains naked battery core by laminating machine lamination, and welding electrode ear, sealing, injection electrolyte, chemical conversion obtain lithium ion
Battery；
Anode pole piece the preparation method comprises the following steps: by nickel cobalt lithium aluminate cathode material, binder, conductive agent and N- crassitude
Ketone is mixed, and anode sizing agent is obtained, and anode sizing agent is coated on aluminium foil using coating machine, uniform coating, drying, roll-in,
Cross cutting, obtains anode pole piece.
Specific embodiment 5
A kind of silicon-carbon cathode slurry, weight percent component raw material include:
A kind of preparation method of silicon-carbon cathode slurry, method include:
Stirred tank is added with water in sodium carboxymethylcellulose to mix, stirred tank rotation revolving speed is 2400rpm, and revolution revolving speed is
26rpm stirs 190min, obtains mixture a；
Multi wall CNT and single wall CNT is added in mixture a and is mixed, stirred tank rotation revolving speed is 2300rpm, and revolution turns
Speed is 27rpm, stirs 125min, obtains mixture b；
Stirring in mixture b, which is added, in the silicon-carbon cathode material of half soaks it sufficiently, and rotation revolving speed is 600rpm, public
Speed of walking around is that 14rpm is added the other half silicon-carbon cathode material and is stirred, stirred tank rotation revolving speed is after stirring 8min
2600rpm, revolution revolving speed are 34rpm, stir 220min, obtain mixture c；
Butadiene-styrene rubber is added in mixture c, stirred tank rotation revolving speed is 1700rpm, and revolution revolving speed is 28rpm, stirring
110min obtains the silicon-carbon cathode slurry that viscosity is 2500mPas.
A kind of cathode pole piece, including porous copper foil and above-mentioned silicon-carbon cathode slurry, the silicon-carbon cathode slurry is uniform
Coated in porous copper foil surface, cathode pole piece is obtained after drying, roll-in, cross cutting.
Wherein, porous copper foil is with a thickness of 20 μm, porosity 30%；The two-sided surface density of cathode pole piece is 150g/m2；It is negative
The compacted density of pole pole piece is 1.2g/cc.
A kind of lithium ion battery, including anode pole piece, diaphragm, electrolyte and above-mentioned cathode pole piece, anode pole piece is born
Pole piece collocation diaphragm in pole obtains naked battery core by laminating machine lamination, and welding electrode ear, sealing, injection electrolyte, chemical conversion obtain lithium ion
Battery；
Anode pole piece the preparation method comprises the following steps: by nickel-cobalt lithium manganate cathode material, binder, conductive agent and N- crassitude
Ketone is mixed, and anode sizing agent is obtained, and anode sizing agent is coated on aluminium foil using coating machine, uniform coating, drying, roll-in,
Cross cutting, obtains anode pole piece.
Comparative example 1
Difference with specific embodiment 2 is silicon-carbon cathode wet end furnish are as follows:
The multi wall CNT of conductive agent is replaced with into conductive black SP, remaining technique and formula are consistent with specific embodiment 2.
Comparative example 2
The difference of this comparative example and specific embodiment 1 is: porous copper foil is 8 μm, porosity 0%；Only change
The porosity of porous copper foil, remaining technique and formula are consistent with specific embodiment 1.
Comparative example 3
The difference of this comparative example and specific embodiment 4 is silicon-carbon cathode wet end furnish are as follows:
The multi wall CNT of conductive agent is replaced with into conductive black SP, remaining technique and formula are consistent with specific embodiment 4.
Comparative example 4:
The difference of this comparative example and specific embodiment 5 is silicon-carbon cathode wet end furnish are as follows:
The multi wall CNT of conductive agent is replaced with into conductive black SP, remaining technique and formula are consistent with specific embodiment 5.
Specific embodiment 1-5 and comparative example are subjected to cathode pole piece expansion rate, cycle performance of lithium ion battery and energy
The comparison of metric density, negative electrode slurry formula and copper foil are all listed one by one, and data are as follows:
By the comparison of specific embodiment 2 and comparative example 1, specific embodiment 4 and the comparison of comparative example 3, specific embodiment 5 with it is right
Ratio 4 compares, and illustrates that multi wall CNT combines the combination better than conductive black and single wall CNT with single wall CNT, especially in cathode pole
In terms of piece expansion rate and cycle performance of lithium ion battery, cathode pole piece expansion rate reduces 3.1%, 3.9%, 5.3 respectively, follows
Improve 7%, 4% and 9% within ring performance 400 weeks.
It is compared by specific embodiment 1 and comparative example 2, illustrates porous copper foil better than non-porous copper foil, cathode pole piece expansion rate
2.2% is reduced, improves 3% within cycle performance 400 weeks, energy density improves 10wh/kg.
Silicon-carbon cathode slurry, the cathode pole piece, lithium ion battery of specific embodiment 1-5 offer, please refer to Fig. 1, cathode pole
Piece manufacturing process, porous copper foil 16 includes copper foil 12, and many holes 11 are provided on copper foil, and silicon-carbon cathode slurry 13 includes silicon-carbon
Negative electrode material 18, single wall CNT15, multi wall CNT14 and binder 17, when Carbon anode slurry 13 is coated on porous copper foil 16, silicon
Carbon negative pole material 18, single wall CNT15 and multi wall CNT14 are attached on porous copper foil 16 by binder 17.Wherein, silicon-carbon is negative
Pole slurry using the compound conductive agent of single wall CNT and multi wall CNT, due to its special line dotted line conductive network can not only provide it is excellent
Elegant electric conductivity, moreover it is possible to hold onto silicon-carbon cathode material particle, inhibit the expansion of negative electrode material particle, silicon-carbon cathode slurry is answered
When used in cathode pole piece, negative terminal surface is reduced due to SEI film destruction recombination and powder of detached caused by expanding repeatedly, to be promoted
The cycle performance of silicon carbon material；Multi wall CNT and single wall CNT are wrapped in cathode particle surface jointly, will not be repeatedly swollen because of cathode
It is swollen and with cathode particle be detached from and so that electric conductivity is deteriorated, this be further ensured that circulation stability.And cathode pole piece uses
The spatial cache that porous copper foil can give the graphite of expansion certain, can equally can be reduced the expansion rate of cathode pole piece to a certain degree, main
If lighter quality can significantly provide the mass energy density of battery core.
It will be apparent that silicon-carbon cathode slurry, cathode pole piece and lithium ion battery that specific embodiment 1-5 is provided, full electricity is swollen
Swollen rate be significantly lower than be using conductive agent single wall CNT, SP and conventional copper foil lithium ion battery, and energy density is also more simultaneously
Height, and conductive agent content is more, and expansion rate is smaller, and cycle performance is better.
The steps in the embodiment of the present invention can be sequentially adjusted, merged and deleted according to actual needs.
It is described in detail herein, applies specific case and the principle of the present invention and embodiment are explained
It states, above embodiments are merely used to help understand method and its core concept of the invention；Meanwhile for the general skill of this field
Art personnel, according to the thought of the present invention, there will be changes in the specific implementation manner and application range, in conclusion this
Description should not be construed as limiting the invention.
It is apparent to those skilled in the art that for convenience and simplicity of description, the system of foregoing description
It with the specific work process of unit, can refer to corresponding processes in the foregoing method embodiment, details are not described herein.
Claims (10)
1. a kind of silicon-carbon cathode slurry, which is characterized in that weight percent component raw material includes:
The conductive agent includes multi wall CNT and single wall CNT.
2. silicon-carbon cathode slurry according to claim 1, it is characterised in that: the active material in the silicon-carbon cathode material
Silicon is one of monomer silicon, silica and the sub- silicon of oxidation or a variety of；Active material carbon in the silicon-carbon cathode material is
One of natural graphite, artificial graphite, composite graphite, soft carbon, hard carbon and carbonaceous mesophase spherules are a variety of.
3. silicon-carbon cathode slurry according to claim 1, it is characterised in that: the mass ratio of the multi wall CNT and single wall CNT
For 1-30.
4. silicon-carbon cathode slurry according to claim 4, it is characterised in that: the single wall CNT length is 5 μm -20 μm；Institute
Stating multi wall CNT length is 2 μm -5 μm.
5. silicon-carbon cathode slurry according to claim 1, it is characterised in that: the thickener is sodium carboxymethylcellulose.
6. silicon-carbon cathode slurry according to claim 1, it is characterised in that: the binder is butadiene-styrene rubber, polypropylene
At least one of acid, polyvinyl alcohol and sodium alginate.
7. a kind of preparation method of silicon-carbon cathode slurry, which is characterized in that method includes:
Stirred tank is added with water in thickener to mix, stirred tank rotation revolving speed is 1500-2500rpm, and revolution revolving speed is 25-
35rpm stirs 180-240min, obtains mixture a；
Multi wall CNT and single wall CNT is added in mixture a and is mixed, stirred tank rotation revolving speed is 1500-2500rpm, and revolution turns
Speed is 25-35rpm, stirs 120-150min, obtains mixture b；
Stirring in mixture b, which is added, in the silicon-carbon cathode material of half soaks it sufficiently, and rotation revolving speed is 500-1000rpm,
Revolution revolving speed is that 10-15rpm is added the other half silicon-carbon cathode material and is stirred after stirring 5-10min, and stirred tank is walked around certainly
Speed is 2000-3000rpm, and revolution revolving speed is 30-40rpm, stirs 200-300min, obtains mixture c；
Binder is added in mixture c, stirred tank rotation revolving speed is 1500-2000rpm, and revolution revolving speed is 25-35rpm, is stirred
60-120min is mixed, the silicon-carbon cathode slurry that viscosity is 2000-4000mPas is obtained.
8. a kind of cathode pole piece, which is characterized in that including any silicon-carbon cathode slurry of porous copper foil and claim 1-6
Material, the silicon-carbon cathode slurry are coated uniformly on porous copper foil surface, obtain cathode pole piece after drying, roll-in, cross cutting.
9. cathode pole piece according to claim 8, it is characterised in that: the porous copper foil is with a thickness of 6-20 μm, porosity
For 5-30%；The two-sided surface density of the cathode pole piece is 150-250g/m2；The compacted density of the cathode pole piece is 1.2-
1.7g/cc。
10. a kind of lithium ion battery, which is characterized in that any including anode pole piece, diaphragm, electrolyte and claim 8-9
The cathode pole piece, the anode pole piece, cathode pole piece collocation diaphragm obtain naked battery core by laminating machine lamination, welding electrode ear,
Sealing, injection electrolyte, chemical conversion, obtain lithium ion battery；
The anode pole piece the preparation method comprises the following steps:
Positive electrode, binder, conductive agent and N-Methyl pyrrolidone are mixed, anode sizing agent is obtained, by anode sizing agent
It is coated on aluminium foil using coating machine, uniform coating, drying, roll-in, cross cutting obtain anode pole piece；
The positive electrode includes one of cobalt acid lithium, nickle cobalt lithium manganate, nickel cobalt lithium aluminate.
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