CN109817946A - Multilayer silicium cathode material and preparation method thereof and lithium ion battery - Google Patents
Multilayer silicium cathode material and preparation method thereof and lithium ion battery Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000010406 cathode material Substances 0.000 title claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000010410 layer Substances 0.000 claims abstract description 114
- 239000011248 coating agent Substances 0.000 claims abstract description 56
- 238000000576 coating method Methods 0.000 claims abstract description 56
- 239000012790 adhesive layer Substances 0.000 claims abstract description 35
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011888 foil Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000003575 carbonaceous material Substances 0.000 claims description 16
- 229960003638 dopamine Drugs 0.000 claims description 15
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 10
- 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 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 9
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 9
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 239000007767 bonding agent Substances 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims description 6
- 238000007906 compression Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000001965 increasing effect Effects 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000012423 maintenance Methods 0.000 claims description 5
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 4
- -1 polyparaphenylene Polymers 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
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000006255 coating slurry Substances 0.000 claims description 2
- 238000003780 insertion Methods 0.000 claims description 2
- 230000037431 insertion Effects 0.000 claims description 2
- 238000013461 design Methods 0.000 abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 239000011889 copper foil Substances 0.000 description 15
- 229920002125 Sokalan® Polymers 0.000 description 13
- 239000000126 substance Substances 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000010703 silicon Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229920001690 polydopamine Polymers 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 229960004502 levodopa Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006299 self-healing polymer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention discloses a kind of multilayer silicium cathode material and preparation method thereof and lithium ion batteries, belong to technical field of lithium batteries.It includes metal foil, it is in turn attached to cathode main functionality layer, conductive coating and the selfreparing nanometer layer of metal foil surface, it further include the nanoscale adhesive layer between metal foil and cathode main functionality layer, and cathode main functionality layer is divided into upper layer and lower layer, conductive coating is filled between lower cathode main functionality layer and upper cathode main functionality layer, the upper and lower end faces of lower cathode main functionality layer are separately connected conductive coating and nanoscale adhesive layer, and the upper and lower end faces of upper cathode main functionality layer are separately connected selfreparing nanometer layer and conductive coating.The multilayer silicium cathode material that the present invention designs solves the problems, such as that cementability is poor between electrode material main body, meanwhile, using the three-dimensional crosslinking structure of selfreparing nanometer glue-line, it can effectively solve the problem that the problem of volume expansion changes in silicon-carbon cathode use process.
Description
Technical field
The present invention relates to silicium cathode materials, belong to technical field of lithium ion, more particularly to a kind of multilayer silicium cathode
Material and preparation method thereof and lithium ion battery.
Background technique
Lithium ion battery is a kind of secondary cell (rechargeable battery), it relies primarily on lithium ion and moves between a positive electrode and a negative electrode
It moves and carrys out work.In charge and discharge process, Li+Insertion and deintercalation back and forth between two electrodes: when charging, Li+From positive deintercalation,
It is embedded in cathode by electrolyte, cathode is in lithium-rich state；It is then opposite when electric discharge.Application of the silicon materials in lithium ion battery,
It relates generally to 2 aspects: nano-silicon being added in negative electrode material, formed silicon-carbon cathode (capacity for improving lithium ion battery), or
Organo-silicon compound are added in person in the electrolytic solution, improve the property of electrolyte.
The shortcomings that silicium cathode material, is also quite obvious, mainly there is two big disadvantages:
1. silicon can cause Si volume expansion 100%~300% during lithium ion is embedded in deintercalation, produced in material internal
Raw biggish internal stress, damages material structure, electrode material falls off on copper foil, while the SEI film of silicon face is continuous
It is repeatedly formed-rupture-to be formed, reduces the electric conductivity and cyclical stability of electrode jointly；
2. silicon is semiconductor, electric conductivity is more far short of what is expected than graphite, causes irreversible degree during lithium ion deintercalation big, into one
Step reduces its coulombic efficiency for the first time.It is, therefore, necessary to solve the volume expansion and charge and discharge for the first time that silicon generates in charge and discharge process
The low problem of electrical efficiency.
In order to reduce the volume expansion of silicium cathode, it is developed SiOxMaterial, compared to pure Si material, volume expansion
It is substantially reduced, is the silicium cathode material and a kind of more silicon of current practice of a kind of better performances with C composite
Material, but the material still has the problem of silicium cathode fails in actual use, research finds failure and Li+It is embedded in speed
And Arrays Aluminum Films in Acid Solution, the more microstructure crucially with Si cathode have close relationship.
Chinese invention patent application (application publication number: CN108511685A, data of publication of application: 2018-09-07) discloses
A kind of anode plate for lithium ionic cell and preparation method thereof containing conductive coating；The negative electrode tab includes copper foil current collector, conductive painting
Layer and negative electrode active material layer, negative electrode active material layer are solidified by negative electrode slurry, and negative electrode slurry includes following substance: 93~
95 parts of graphite, 1.5~2.5 parts of conductive black SP, 1~2 part of sodium carboxymethylcellulose, 2~3 parts of butadiene-styrene rubber, 130
~150 parts of deionized water；Conductive coating is solidified by electrocondution slurry, and electrocondution slurry includes following substance: compounded carbons 10
~95 parts, 5~50 parts of binder, 5~40 parts of dispersing agent, 450~550 parts of organic solvent.The present invention by applying on a current collector
One layer of special electrocondution slurry is covered, large specific surface area, impedance is small, can greatly improve pole piece cohesive force, enhances electric conductivity, and subtract
Few binder and conductive agent additive amount, improve the energy density of battery.However the design of this application has ignored electrode material main body
Between cementability.
Chinese invention patent application (application publication number: CN109216654 A, data of publication of application: 2019-01-15) is open
The lithium ion battery of a kind of multilayer cathode pole piece and its preparation method and application, wherein the multilayer cathode pole piece, including metal
The surface of foil collector, the metal foil collector is coated with conductive coating；The surface of the conductive coating is coated with main body function
Ergosphere；The surface of the main functionality layer is coated with graphite linings.In addition, the invention also discloses a kind of systems of multilayer cathode pole piece
Preparation Method and its lithium ion battery of preparation.A kind of lithium of multilayer cathode pole piece disclosed by the invention and its preparation method and application
Ion battery, the charge efficiency high and low temperature charging and discharging capabilities which has are strong, can significantly improve lithium ion battery
High rate charge-discharge performance, extend the high rate charge-discharge inferior pole piece service life, be conducive to improve cell production companies product city
Field application prospect, is of great practical significance.However, the design of this application has ignored the variation of electrode body material volume
Adhesive property is deteriorated, material pulverizing problem.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of multilayer silicium cathode material and preparation method thereof and lithium ions
Battery.The multilayer silicium cathode material that the present invention designs increases nanoscale adhesive layer between cathode main functionality layer and metal foil,
Solve the problems, such as that cementability is poor between electrode material main body, meanwhile, selfreparing is also bonded in cathode main functionality layer surface
Nanometer glue-line can effectively solve the problem that volume in silicon-carbon cathode use process using the three-dimensional crosslinking structure of selfreparing nanometer glue-line
The problem of expansion variation.
To achieve the above object, the invention discloses a kind of multilayer silicium cathode materials, it includes metal foil, is in turn attached to
Cathode main functionality layer, conductive coating and the selfreparing nanometer layer of the metal foil surface, further include be located at the metal foil with
Nanoscale adhesive layer between cathode main functionality layer, and the cathode main functionality layer is divided into upper layer and lower layer, the conductive painting
Layer is filled between lower cathode main functionality layer and upper cathode main functionality layer, the upper and lower ends of the lower cathode main functionality layer
Face is separately connected conductive coating and nanoscale adhesive layer, and the upper and lower end faces of the upper cathode main functionality layer, which are separately connected, to be reviewed one's lessons by oneself
Multiple nanometer layer and conductive coating.
Preferably, the metal foil is copper foil.
Preferably, the copper foil with a thickness of 6~8 μm, constitute cathode pole piece collector.
The nanoscale adhesive layer is that the dopamine that concentration is 0.5~2.5mg/mL is made up of autohemagglutination, thickness 2~
Tridimensional network between 100nm.By the way that the concentration of dopamine is set to be constant range, nanoscale can be formed in coating
Other poly-dopamine.
Preferably, nanoscale adhesive layer has at least one of network structure or rectangular lattice structure.
Further, the conductive coating by mass percent be in terms of including 25%~75% electrically conducting adhesive, 10%~
Three-dimensional conductive network of the thickness that 30%PVDF and 15%~35%PAA is constituted between 2~150nm；The electrically conducting adhesive
Including at least one of poly-phenylene vinylene (ppv) or derivatives thereof, polyparaphenylene's acetylene or derivatives thereof, wherein polyparaphenylene's second
The electric conductivity of alkene and polyparaphenylene's acetylene is good.The electric conductivity of its derivative is also preferable, in the cementation of PAA, PVDF film forming
Under effect, the film layer for having certain caking property and satisfactory electrical conductivity is formed, specific includes the chemical combination for having following structural formula
Object.
Wherein, R group is-C in above-mentioned Formulas I -2, Formulas I -4 and Formulas I -68H17、OC8H18、OC8H16One of.
Preferably, the conductive coating by mass percent be in terms of including 35%~65% electrically conducting adhesive, 15%~
30%PVDF and 20%~35%PAA.
It is optimal, the conductive coating by mass percent be in terms of including 50% electrically conducting adhesive, 20%PVDF and 30%
PAA。
And PVDF is the abbreviation of Kynoar in chemical field, PAA is the abbreviation of polyacrylic acid in chemical field.
Preferably, conductive coating has at least one of network structure or rectangular lattice structure.
Further, the intramolecular of the selfreparing nanometer layer forms hydrogen bond.Advantageously ensure that the rock-steady structure of negative electrode tab,
And selfreparing nanometer layer with a thickness of 2~150nm.
The molecule of the selfreparing nanometer layer is formed mainly by having the compound A and diethylidene of following chemical structural formula
Triamine and urea reaction obtain.
Wherein, compound A is dicarboxylic acids or tricarboxylic acid.
Concrete structure formula is as follows:
Particularly modus ponens A-I reacts under 120 ° with the mixture (40%:60%) of formula A-II with diethylenetriamines
2h, then be warming up under 160 ° of nitrogen protections to react and obtain product for 24 hours, then itself and urea are mixed to get in ethyl alcohol with 100:1
Selfreparing nanometer slurries are coated on silicon-carbon electrode surface using intaglio plate technology, are toasted, form intermolecular three-dimensional cross-linked knot
Structure.To be conducive to safeguard the stability of silicon carbon material volume.
Preferably, selfreparing nanometer layer has at least one of network structure or rectangular lattice structure.
Further, the main functionality layer by mass percent be in terms of including 95%~97% silicon carbon material, 0.8%~
1.2% conductive black, 0.5%~1% carbon nanotube, 1%~1.8% bonding agent and 1% sodium carboxymethylcellulose, the bonding
Agent is one of PAA or sodium alginate.
Preferably, the main functionality layer by mass percent be in terms of including 96% silicon carbon material, 1% conductive black,
0.5% carbon nanotube, 1.5% bonding agent and 1% sodium carboxymethylcellulose.
Further, the silicon carbon material includes cladded type or embedded type Si-C composite material, has good conduction
Property.
Preferably, the silicon carbon material includes carbon coating silicon carbon material, porous Si-C composite material, silicon/agraphitic carbon/stone
One of black ternary complex based material.
In order to preferably realize technical purpose of the invention, the invention also discloses the preparations of above-mentioned multilayer silicium cathode material
Method includes the following steps:
1) it takes the Tris-HCl slurries of dopamine to be coated on metal foil surface using gravure application, obtains net after dry
Shape nanoscale adhesive layer；
2) silicon carbon material, conductive black, carbon nanotube, bonding agent and sodium carboxymethylcellulose and solvent is taken to be mixed to form negative
Pole main functionality material slurry is coated on the mesh nano grade tie layer surface of step 1), after toasted, room temperature roll process,
Cathode main functionality layer must be descended, and compression ratio is 5%~15% after roll-in；
3) conductive coating slurries are coated using gravure application in the lower cathode main functionality layer surface of step 2), it is dry
The conductive coating of reticular structure is obtained afterwards；
4) continue step 3) conductive coating surface coating step 2) cathode main functionality material slurry, it is toasted,
After room temperature roll process, cathode main functionality layer is obtained, and compression ratio is 5%~25% after roll-in；
5) selfreparing nanometer slurries are coated using gravure application in the upper cathode main functionality layer surface of step 4), done
The selfreparing nanometer layer of reticular structure is obtained after dry.
Further, the concentration of the Tris-HCl slurries of the dopamine is 0.5~2.5mg/mL.
Preferably, the concentration of the Tris-HCl slurries of the dopamine is 1.0~1.5mg/mL.
Preferably, the concentration of the Tris-HCl slurries of the dopamine is 1.2mg/mL.
Preferably, 80~120m/min of coating speed in step 1).
Optimal, coating speed 100m/min in step 1).
Preferably, dry in step 1) is to be placed in air drying 2h.
Further, the baking of the step 2) or step 4) are as follows: by 45 DEG C of gradient increased temperatures to 85 DEG C of 5~10min of maintenance
Afterwards, then gradient cooling is to 30 DEG C, and heating or rate of temperature fall are 10 DEG C/min, makes PAA and poly-dopamine adhesive layer in silicon-carbon coating
Sufficiently reaction.
Preferably, 60~80m/min of coating speed in the step 2) or step 4).
Optimal, coating speed 70m/min in the step 2) or step 4).
Preferably, the baking is to be toasted using baking oven.Preferably, compression ratio is after the roll-in of cathode main functionality layer
10%~15%.
Preferably, compression ratio is 12% after the roll-in of cathode main functionality layer.
Preferably, the solvent in step 2) is N-Methyl pyrrolidone.
Preferably, 80~120m/min of coating speed in the step 3).
Preferably, dry dry to be placed under 50 DEG C of environment in the step 3).
Preferably, the solid content of selfreparing nanometer slurries is 2%~20% in the step 5).
Optimal, the solid content of selfreparing nanometer slurries is 10%~15% in the step 5).
Preferably, dry in the step 5) is 60 DEG C of vacuum dryings.
Wherein, Tris-HCl is the hydrochloric acid solution of trishydroxymethylaminomethane in chemical field.
At the same time, the invention also discloses a kind of lithium ion battery, its cathode pole piece includes using claim 1 institute
The multilayer silicium cathode material stated.Particularly above-mentioned cathode pole piece and isolation film, ternary nickle cobalt lithium manganate anode pole piece are passed through
Lithium ion battery is made in the processes such as assembling, fluid injection, chemical conversion.
The present invention passes through inside using the carboxyl of acrylic acid in the amino and cathode main functionality layer of dopamine in adhesive layer
Network crosslinks, and enhances the combination between each layer；The present invention is using between amido bond in selfreparing nanometer layer
Hyarogen-bonding, and its Hyarogen-bonding and itself and conductive coating between the carboxyl of acrylic acid in cathode main functionality layer
Hyarogen-bonding between the carboxyl of middle acrylic acid, on the basis of enhancing binding force between each layer, by silicon carbon material confinement one
Determine in volume, can solve to influence battery conductive because of volume expansion variation in silicon-carbon cathode use process to a certain extent
And the problem of cyclical stability.
Cathode main functionality layer is divided into upper layer and lower layer by present invention design, and imports conductive coating between the two layers, phase
With the conductive area for increasing silicon-carbon cathode material under design condition, be conducive to the electric conductivity for promoting material.
Each substance may be designed as nanometer in nanoscale adhesive layer, conductive coating and the selfreparing nanometer layer that the present invention designs
Size, therefore can guarantee the thickness requirement of entire cathode pole piece.
It is provided with reticular structure in nanoscale adhesive layer, conductive coating and the selfreparing nanometer layer that the present invention designs, therefore can
Guarantee effective transmitting of ion, electronics etc..
The beneficial effects are mainly reflected as follows following aspects:
1, present invention design coats dopamine adhesive layer on negative current collector surface, in entire pole piece heat drying process
In, the binder in cathode main functionality layer is crosslinked with dopamine to react so that the adhesion strength between each layer obtain into
One step is reinforced, and the extent of exfoliation of silicon carbon material is reduced；
2, adhesive layer, conductive coating and the selfreparing nanometer layer that the present invention designs are provided with reticular structure, not only contribute to
Ion, electron transmission in battery use process are conducive to the electric conductivity for promoting silicon carbon material, while also can effectively solve silicon-carbon
The problem of influencing battery conductive and cyclical stability because of volume expansion variation in cathode use process；
3, each layer for having different function for the cathode pole piece material that the present invention designs is by being alternately coated in afflux body surface
Face, by multiple roll-in, fits closely on the basis of realizing that different function combines between each material, so that entire pole piece is negative
Pole material is frivolous, and without rebound.
Detailed description of the invention
Fig. 1 is the partial sectional view for the multilayer silicium cathode material that the present invention designs；
Fig. 2 is the peel strength test figure that negative electrode material is made in the embodiment of the present invention；
Fig. 3 is the conducting performance test figure that negative electrode material is made in the embodiment of the present invention；
Wherein, above-mentioned figure label is as follows:
Metal foil 1, nanoscale adhesive layer 2, cathode main functionality layer 3 are (wherein: lower cathode main functionality layer 3.1, upper cathode
Main functionality layer 3.2), conductive coating 4, selfreparing nanometer layer 5.
Specific embodiment
In order to better explain the present invention, below in conjunction with the specific embodiment main contents that the present invention is furture elucidated, but
The contents of the present invention are not limited solely to following embodiment.
Embodiment 1
Present embodiment discloses the preparation methods of multilayer silicium cathode material, include the following steps:
1) the Tris-HCl slurries that concentration is the dopamine of 2mg/mL is taken to be coated on using gravure application with a thickness of 8 μm
1 surface of copper foil shown in FIG. 1, formed after dry with a thickness of 2nm, the network nanoscale bonding of length × wide=3mm × 3mm
Layer 2；
2) taking mass fraction is 96 parts of carbon coating silicon carbon materials, 1 part of conductive black, 0.8 part of carbon nanotube, 1.2 parts poly- third
Olefin(e) acid and 1 part of sodium carboxymethylcellulose and solvent N-methyl pyrilidone are mixed to form the cathode main functionality that solid content is 48%
Material slurry is coated on 2 surface of network nanoscale adhesive layer of step 1), via 45 DEG C of gradient increased temperatures to 85 DEG C of maintenances 5
~after ten minutes, then gradient cooling, to 30 DEG C, heating or rate of temperature fall are 10 DEG C/min, make PAA and poly- DOPA in silicon-carbon coating
Amine adhesive layer sufficiently reacts, and room temperature roll-in 1 time, obtains the lower cathode main functionality layer 3.1 with a thickness of 40 μm；
3) gravure application coating solid content is used to lead for 15% in lower 3.1 surface of cathode main functionality layer of step 2)
Electric polymer slurries are grown × wide=3mm × 3mm after 35 DEG C of drying, are applied with a thickness of the conductive of network structure of 2nm
Layer 4；
4) continue step 3) 4 surface coating step 2 of conductive coating) cathode main functionality material slurry oven drying
Afterwards, room temperature roll-in 1 time obtains the upper cathode main functionality layer 3.2 with a thickness of 40 μm；
5) use gravure application coating solid content for 12% in upper 3.2 surface of cathode main functionality layer of step 4)
Self-healing polymers slurries, through room temperature roll-in, obtain the selfreparing nanometer with a thickness of 2nm of network structure after 60 DEG C of drying
Layer 5.The multilayer silicium cathode material that integral thickness is about 110 μm is finally prepared.As shown in Figure 1, showing only the one of copper foil 1
Each layer on a surface, actually in the upper and lower surfaces of copper foil 1 successively symmetrical nanoscale adhesive layer 2, lower cathode main body
Functional layer 3.1, conductive coating 4, upper cathode main functionality layer 3.2 and selfreparing nanometer layer 5.
Embodiment 2
Present embodiment discloses the preparation method of multilayer silicium cathode material, preparation step and each parameter with embodiment 1, in addition to
Polyacrylic acid is replaced with into sodium alginate in step 2).
Embodiment 3
Present embodiment discloses the preparation methods of multilayer silicium cathode material, viscous without the network nanoscale of step 1)
The preparation of layer 2 is tied, the cathode main functionality layer 3.1 in the case where 1 surface of copper foil is directly formed, in addition to this, other steps and parameter are equal
It is identical.
Embodiment 4
Present embodiment discloses the preparation methods of multilayer silicium cathode material, include the following steps:
1) Tris-HCl that concentration is the dopamine of 2mg/mL is taken to be coated on the figure with a thickness of 8 μm using gravure application
1 surface of copper foil shown in 1 is formed after dry with a thickness of 2nm, the network nanoscale adhesive layer 2 of length × wide=3mm × 3mm；
2) taking mass fraction is 96 parts of carbon coating silicon carbon materials, 1 part of conductive black, 0.8 part of carbon nanotube, 1.2 parts poly- third
Olefin(e) acid and 1 part of sodium carboxymethylcellulose and solvent N-methyl pyrilidone are mixed to form the cathode main functionality that solid content is 48%
Material slurry is coated on 2 surface of network nanoscale adhesive layer of step 1), via 45 DEG C of gradient increased temperatures to 85 DEG C of maintenances 5
After~10min, then gradient cooling, to 30 DEG C, heating or rate of temperature fall are 10 DEG C/min, make PAA and poly-dopamine in silicon-carbon coating
Adhesive layer sufficiently reacts, and room temperature roll-in 1 time, obtains the cathode main functionality layer 3 with a thickness of 80 μm；
3) gravure application coating solid content is used to review one's lessons by oneself for 12% in 3 surface of cathode main functionality layer of step 2)
Multiple polymer slurries, through room temperature roll-in, obtain the selfreparing nanometer layer 5 with a thickness of 2nm of network structure after 60 DEG C of drying.
The multilayer silicium cathode material that integral thickness is about 110 μm is finally prepared.As shown in Figure 1, showing only a table of copper foil 1
Each layer on face, actually in the upper and lower surfaces of copper foil 1 successively symmetrical nanoscale adhesive layer 2, cathode main functionality layer
3 and selfreparing nanometer layer 5.
Embodiment 5
Present embodiment discloses the preparation methods of multilayer silicium cathode material, include the following steps:
1) Tris-HCl that concentration is the dopamine of 2mg/mL is taken to be coated on the figure with a thickness of 8 μm using gravure application
1 surface of copper foil shown in 1 is formed after dry with a thickness of 2nm, the network nanoscale adhesive layer 2 of length × wide=3mm × 3mm；
2) taking mass fraction is 96 parts of carbon coating silicon carbon materials, 1 part of conductive black, 0.8 part of carbon nanotube, 1.2 parts poly- third
Olefin(e) acid and 1 part of sodium carboxymethylcellulose and solvent N-methyl pyrilidone are mixed to form the cathode main functionality that solid content is 48%
Material slurry is coated on 2 surface of network nanoscale adhesive layer of step 1), via 45 DEG C of gradient increased temperatures to 85 DEG C of maintenances 5
After~10min, then gradient cooling, to 30 DEG C, heating or rate of temperature fall are 10 DEG C/min, make PAA and poly-dopamine in silicon-carbon coating
Adhesive layer sufficiently reacts, and room temperature roll-in 1 time, obtains the lower cathode main functionality layer 3.1 with a thickness of 40 μm；
3) gravure application coating solid content is used to lead for 15% in lower 3.1 surface of cathode main functionality layer of step 2)
Electric polymer slurries are grown × wide=3mm × 3mm after 35 DEG C of drying, are applied with a thickness of the conductive of network structure of 2nm
Layer 4；
4) continue 4 surface coating step 2 of conductive coating in step 3)) cathode main functionality material slurry, baking oven is dry
After dry, 1 roll-in of room temperature obtains the upper cathode main functionality layer 3.2 with a thickness of 40 μm；Integral thickness finally, which is prepared, is about
110 μm of multilayer silicium cathode material.As shown in Figure 1, each layer on a surface of copper foil 1 is shown only, actually in copper foil 1
Upper and lower surfaces successively symmetrical nanoscale adhesive layer 2, lower cathode main functionality layer 3.1, conductive coating 4, upper cathode master
Body function layer 3.2 and selfreparing nanometer layer 5.
Wherein, the embodiment of the present invention 1, embodiment 2 be using design scheme of the present invention obtain have complete structure
Negative electrode material, nanoscale adhesive layer is not designed on negative electrode material surface in embodiment 3, and negative electrode material surface will be upper and lower in embodiment 4
Cathode main functionality design of material is individual 1 layer, and selfreparing nanometer layer is not designed on negative electrode material surface in embodiment 5.
By above-described embodiment 1~5 prepare multilayer silicium cathode material remove respectively, obtain peel strength as shown in Fig. 2,
The addition of nanoscale adhesive layer and selfreparing nanometer layer can effectively improve between copper foil and main body active material as seen from Figure 2
Adhesion strength.
Use two probe pole piece overall resistivities direct respectively multilayer silicium cathode material prepared by above-described embodiment 1~5
Mensuration measures pole piece resistivity, as a result as Fig. 3 is designed to compared to original independent 1 layer of cathode main functionality material
After 2 layers, conductive capability is greatly improved.
Continue by five cathode pole pieces and ternary nickle cobalt lithium manganate anode pole piece, isolation film by winding, assembly, fluid injection,
Full battery is made in the processes such as chemical conversion.Battery 1C charge-discharge test, charging/discharging voltage 2.75~4.2V of range, as the following table 1 is shown
Each cycle performance of battery test result, wherein every class value is to be averaged after testing 5 times respectively.When in cathode main functionality material
Containing acrylic acid, and it is designed to have present invention structure shown in FIG. 1, capacity retention ratio is most after repeatedly recycling
It is high.
Table 1
| Project | Capacity retention ratio % after 0.5C/0.5C 600 times circulations |
| Embodiment 1 | 89.4 |
| Embodiment 2 | 83.1 |
| Embodiment 3 | 63.7 |
| Embodiment 4 | 71.2 |
| Embodiment 5 | 76.4 |
It follows that though the addition of nanoscale adhesive layer can slightly increase the resistivity of pole piece, in nanoscale adhesive layer
Poly-dopamine and cathode main functionality layer in polyacrylic acid be capable of forming cross-linked structure, further enhance pole piece cementability
Can, while the cross-linked structure based on selfreparing nanometer layer hydrogen bond can sufficiently buffer the change of the volume in silicon-carbon cathode use process
Change, synthesis improves the cycle performance of battery.
Above embodiments are only best citing, rather than a limitation of the embodiments of the present invention.Except above-described embodiment
Outside, there are also other embodiments by the present invention.All technical solutions formed using equivalent substitution or equivalent transformation, all fall within the present invention
It is required that protection scope.
Claims (10)
1. a kind of multilayer silicium cathode material, it includes metal foil (1), is in turn attached to the cathode master on the metal foil (1) surface
Body function layer (3), conductive coating (4) and selfreparing nanometer layer (5) further include being located at the metal foil (1) and cathode main body function
Nanoscale adhesive layer (2) between ergosphere (3), and the cathode main functionality layer (3) is divided into upper layer and lower layer, the conductive coating
(4) it is filled between lower cathode main functionality layer (3.1) and upper cathode main functionality layer (3.2), the lower cathode main functionality
The upper and lower end faces of layer (3.1) are separately connected conductive coating (4) and nanoscale adhesive layer (2), the upper cathode main functionality layer
(3.2) upper and lower end faces are separately connected selfreparing nanometer layer (5) and conductive coating (4).
2. multilayer silicium cathode material according to claim 1, it is characterised in that: the nanoscale adhesive layer (2) is for concentration
The dopamine of 0.5~2.5mg/mL is made up of autohemagglutination, tridimensional network of the thickness between 2~100nm.
3. multilayer silicium cathode material according to claim 1 or claim 2, it is characterised in that: the conductive coating (4) is with quality percentage
Than for count include the thickness that constitutes of 25%~75% electrically conducting adhesive, 10%~30%PVDF and 15%~35%PAA 2~
Three-dimensional conductive network between 150nm；The electrically conducting adhesive includes poly-phenylene vinylene (ppv) or derivatives thereof, polyparaphenylene's acetylene
At least one of or derivatives thereof.
4. multilayer silicium cathode material according to claim 1 or claim 2, it is characterised in that: the molecule of the selfreparing nanometer layer (5)
Interior formation hydrogen bond.
5. multilayer silicium cathode material according to claim 1 or claim 2, it is characterised in that: the main functionality layer (3) is with quality hundred
Point than for meter include 95%~97% silicon carbon material, 0.8%~1.2% conductive black, 0.5%~1% carbon nanotube, 1%~
1.8% bonding agent and 1% sodium carboxymethylcellulose, the bonding agent are one of PAA or sodium alginate.
6. multilayer silicium cathode material according to claim 5, it is characterised in that: the silicon carbon material includes cladded type or insertion
Type Si-C composite material.
7. the preparation method of multilayer silicium cathode material, includes the following steps: described in a kind of claim 1
1) it takes the Tris-HCl slurries of dopamine to be coated on metal foil (1) surface using gravure application, obtains net after dry
Shape nanoscale adhesive layer (2)；
2) silicon carbon material, conductive black, carbon nanotube, bonding agent and sodium carboxymethylcellulose and solvent is taken to be mixed to form cathode master
Body function material slurry is coated on mesh nano grade adhesive layer (2) surface of step 1), after toasted, room temperature roll process, obtains
Lower cathode main functionality layer (3.1), and compression ratio is 5%~25% after roll-in；
3) conductive coating slurries are coated using gravure application in lower cathode main functionality layer (3.1) surface of step 2), done
The conductive coating (4) of reticular structure is obtained after dry；
4) continue step 3) conductive coating (4) surface coating step 2) cathode main functionality material slurry, it is toasted, normal
Warm roll-in must go up cathode main functionality layer (3.2), and compression ratio is 5%~25% after roll-in；
5) selfreparing nanometer slurries are coated using gravure application in upper cathode main functionality layer (3.2) surface of step 4),
The selfreparing nanometer layer (5) of reticular structure is obtained after drying.
8. the preparation method of multilayer silicium cathode material according to claim 7, it is characterised in that: the step 2) or step 4)
Baking are as follows: after 45 DEG C of gradient increased temperatures to 85 DEG C of 5~10min of maintenance, then gradient cooling is to 30 DEG C, wherein heating or cooling speed
Rate is 10 DEG C/min.
9. according to the preparation method of the multilayer silicium cathode material of claim 7 or 8, it is characterised in that: the dopamine
The concentration of Tris-HCl slurries is 0.5~2.5mg/mL.
10. a kind of lithium ion battery, its cathode pole piece includes using multilayer silicium cathode material described in claim 1.
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