CN105489898B - Conductive aqueous binders and preparation method thereof, lithium ion battery - Google Patents
Conductive aqueous binders and preparation method thereof, lithium ion battery Download PDFInfo
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- CN105489898B CN105489898B CN201511032994.6A CN201511032994A CN105489898B CN 105489898 B CN105489898 B CN 105489898B CN 201511032994 A CN201511032994 A CN 201511032994A CN 105489898 B CN105489898 B CN 105489898B
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- 239000011230 binding agent Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 153
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 74
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 74
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 67
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 39
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 21
- 239000012266 salt solution Substances 0.000 claims abstract description 19
- 230000001427 coherent effect Effects 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 17
- 239000000460 chlorine Substances 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical group CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 13
- 239000000661 sodium alginate Substances 0.000 claims description 13
- 235000010413 sodium alginate Nutrition 0.000 claims description 13
- 229940005550 sodium alginate Drugs 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 239000002322 conducting polymer Substances 0.000 claims description 10
- 229920001940 conductive polymer Polymers 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 9
- 239000000737 potassium alginate Substances 0.000 claims description 8
- 235000010408 potassium alginate Nutrition 0.000 claims description 8
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 241000446313 Lamella Species 0.000 claims description 4
- 239000002079 double walled nanotube Substances 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002048 multi walled nanotube Substances 0.000 claims description 4
- 238000009938 salting Methods 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 241001474374 Blennius Species 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 29
- 230000008569 process Effects 0.000 description 14
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000011149 active material Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 7
- 238000005476 soldering Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000006182 cathode active material Substances 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000002109 single walled nanotube Substances 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical class ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000011366 tin-based material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect 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
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of conductive aqueous binders and preparation method thereof, lithium ion battery.Conductive aqueous binders include graphene, carbon nanotube, cross-linked polymer and polyvalent metal ion water-soluble salt solution, wherein, graphene and carbon nanotube form three-dimensional conductive network structure by chemical bonding with cross-linked polymer respectively, and cross-linked polymer and polyvalent metal ion water-soluble salt solution are cross-linked to form three-dimensional coherent network structure.By the above-mentioned means, the present invention can effectively improve the adhesion strength of binder, while lithium ion battery can be made while there is high-energy density, long circulating, fast charge, high security advantage.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular to a kind of conduction aqueous binders and preparation method thereof, lithium from
Sub- battery.
Background technique
With the continuous development of New Energy Industry, lithium ion battery is as green, environmentally friendly new energy in digital class
Product, electric tool class product, electric car, electric bus are widely used on heavy-duty car, not with application
Disconnected extension, more stringent requirements are proposed for energy density and security performance of the people to lithium ion battery.
Binder has a very important significance in Modern electrochemistry device, although it is not the electro-chemical activity of battery
Ingredient is the important component that electrode active material is closely joined together.The mechanical property and electrochemistry of binder itself
Stability also has significant impact to the overall performance of battery.Current battery industry is commonly bonded with two types: a kind of
It is linear polymeric binder, including vinylidene (PVDF), sodium carboxymethylcellulose (CMC) etc., uses technology maturation, bonding
The performance of agent itself is stablized, but using this binder prepares electrode slice and need to consume a large amount of N-Methyl pyrrolidones (NMP) and have
Solvent, price is high, causes serious pollution to the environment.Another kind is point type binder, such as butadiene-styrene rubber (SBR) lotion, polytetrafluoroethylene (PTFE)
(PTFE) lotion, this kind of binder lack long-range cementing property, and it is bad that there are mechanical performances, tensile strength it is not high and also this from
The resistance of body is high, unfavorable to the long-term cycle performance and high-rate charge-discharge capability of battery.
How the comprehensive performance of binder a kind of is provided, so that reducing usage amount while improving binder adhesion strength
With polarization of electrode internal resistance, extend the service life of battery, becoming there are important technological problems to be solved.
Summary of the invention
The invention mainly solves the technical problem of providing a kind of conductive aqueous binders and preparation method thereof, lithium-ion electric
Pond, can effectively improve the adhesion strength of binder, while be applied to lithium ion battery, can make lithium ion battery while have
There are high-energy density, long circulating, fast charge, high security advantage.
In order to solve the above technical problems, one technical scheme adopted by the invention is that: a kind of conductive aqueous binders are provided,
The conduction aqueous binders include graphene, carbon nanotube, cross-linked polymer and polyvalent metal ion water-soluble salt solution,
Wherein, the graphene and the carbon nanotube form three-dimensional conductive net by chemical bonding with the cross-linked polymer respectively
Network structure, the cross-linked polymer and the polyvalent metal ion water-soluble salt solution are cross-linked to form three-dimensional coherent network structure.
Wherein, the graphene and the carbon nanotube contain at least one in hydroxyl, carboxyl and chlorine acyl group for surface
The graphene and carbon nanotube of kind；The cross-linked polymer is at least one of sodium alginate and potassium alginate；It is described more
Valence metal ion water-soluble salt solution is Ca2+、Al3+、Ba2+、Zn2+、Fe3+、Cu2+At least one of water soluble salt.
Wherein, in the conductive aqueous binders, the mass percentage content of the cross-linked polymer is 5-50%, described
The mass percentage content of graphene is 0.1-5%, and the carbon nanotube mass degree is 0.3-15%, the multivalence
Metal ion water soluble salt and the cross-linked polymer mass ratio are a, wherein 0 < a < 0.5.
Wherein, the carbon nanotube is that single-walled carbon nanotube, double-walled carbon nano-tube, multi-walled carbon nanotube and beamforming carbon are received
At least one of mitron；Wherein, the carbon nanotube has the diameter and 30-100 μm of length of 5-50nm；The graphene
Lamella be single layer and/or 2-8 layers.
Wherein, the viscosity of the conductive aqueous binders is 200-20000mPa.s.
In order to solve the above technical problems, another technical solution used in the present invention is: providing a kind of aqueous bonding of conduction
The preparation method of agent, which comprises the graphene and carbon nanotube with functional group, mixing are added into cross-linked polymer
Form conducting polymer；Be added polyvalent metal ion salting liquid into the conducting polymer, stirring crosslinking react to be formed it is described
Conductive aqueous binders.
Wherein, the functional group is at least one of carboxyl, hydroxyl and chlorine acyl group, it is described into cross-linked polymer plus
Enter graphene and carbon nanotube with functional group, be mixed to form before conducting polymer, further includes: to the graphene and institute
It states carbon nanotube and carries out surface preparation, so that the graphene and the carbon nano tube surface is contained carboxyl and hydroxyl, then lead to
Crossing thionyl chloride effect makes the carboxyl be modified as chlorine acyl group, so that the graphene and carbon described in being formed with functional group are received
Mitron.
Wherein, the cross-linked polymer is at least one of sodium alginate and potassium alginate；The polyvalent metal from
Sub- water-soluble salt solution is Ca2+、Al3+、Ba2+、Zn2+、Fe3+、Cu2+At least one of water soluble salt；The conduction is aqueous viscous
It ties in agent, the mass percentage content of the cross-linked polymer is 5-50%, and the mass percentage content of the graphene is
0.1-5%, the carbon nanotube mass degree are 0.3-15%, the polyvalent metal ion water soluble salt and the friendship
Linked polymer mass ratio is a, wherein 0 < a < 0.5.
In order to solve the above technical problems, another technical solution used in the present invention is: providing a kind of lithium ion battery, institute
It states lithium ion battery to be made of lithium ion battery negative electrode, anode pole piece, diaphragm, electrolyte and shell, wherein the lithium
Ion battery cathode pole piece is that conductive aqueous binders described above and the slurry of negative electrode active material mixed configuration are coated
And it dries and to be formed.
Wherein, in the slurry, the quality of the conduction aqueous binders is the 0.5- of the slurry solids gross mass
10%.
The beneficial effects of the present invention are: being in contrast to the prior art, conduction aqueous binders packet provided by the invention
Include graphene, carbon nanotube, cross-linked polymer and polyvalent metal ion water-soluble salt solution, wherein graphene and carbon nanometer
Pipe forms three-dimensional conductive network structure, cross-linked polymer and polyvalent metal ion by chemical bonding with cross-linked polymer respectively
Water-soluble salt solution is cross-linked to form three-dimensional coherent network structure.Conductive aqueous binders of the invention are applied to lithium-ion electric
Pond can effectively improve battery entirety by the three-dimensional coherent network structure and three-dimensional conductive network structure collective effect of binder
Conductivity and improvement battery long circulating and high rate performance.
Detailed description of the invention
Fig. 1 is a kind of flow chart of the preparation method of conductive aqueous binders provided in an embodiment of the present invention；
Fig. 2 is the embodiment of the present invention 1, embodiment 2 and the circulation comparison diagram of lithium ion battery made from comparative example 1.
Specific embodiment
Hereinafter, in conjunction with specific embodiments and attached drawing the present invention is described in detail, it should be noted that this following hair
The specific substance being previously mentioned in bright embodiment is intended only as a kind of illustrate and is illustrated, is not limited thereto, i.e. the same terms
Under, it can also be substituted with other similar substances of specific substance cited in the embodiment of the present invention and realize technical side of the invention
Case, the present invention without illustrating one by one.Those skilled in the art use in the case where not needing to make the creative labor
Substance listed by the embodiment of the present invention is similar or structure is similar other substances realize the present invention, also belong to what the present invention protected
Range.
The embodiment of the present invention provides a kind of conductive aqueous binders, which includes graphene, carbon nanometer
Pipe, cross-linked polymer and polyvalent metal ion water-soluble salt solution, wherein the conductive aqueous binders of the embodiment of the present invention have
There is three-dimensional net structure, wherein three-dimensional net structure is as made of polymer and the crosslinking of polyvalent metal ion water-soluble salt solution
Three-dimensional coherent network structure and the three-dimensional conductive network formed with the graphene of polymer-bound and carbon nanotube are constituted.
Wherein, implementation as one preferred, graphene are preferably that surface is contained in hydroxyl, carboxyl and chloramines base
One or more kinds of graphenes, carbon nanotube is preferably that one of hydroxyl, carboxyl and chloramines base or more are contained in surface
The carbon nanotube of kind.Can during the preparation process, graphene and carbon nanotube pass through strong oxidizing property strong acid treatment before the use
Or its surface is set to contain carboxyl, hydroxyorgano group through high-temperature process by the mixed gas with oxidation effectiveness.
Wherein, as an example, the cross-linked polymer of the embodiment of the present invention can be sodium alginate and potassium alginate
In one of which or two kinds of combination, polyvalent metal ion water-soluble salt solution be Ca2+、Al3+、Ba2+、Zn2+、Fe3+、Cu2 +One of or a variety of combination in water soluble salt.Wherein, it is preferred to use Ca2+Water soluble salt.
Wherein, implementation as one preferred, in conductive aqueous binders, the mass percent of cross-linked polymer
Content is 5%-50%, such as 10%, 15%, 20%, 25%, 40%, 45% etc., the mass percentage content of graphene is
0.1%-5%, such as 0.3%, 0.5%, 1%, 3%, 4% etc., the mass percentage content of carbon nanotube is 0.3%-
15%, such as 0.5%, 1.5%, 2%, 5%, 8%, 10%, 12% etc., the quality of polyvalent metal ion water soluble salt and poly-
The ratio for closing amount of substance is a, 0 < a < 0.5.For example the mass ratio of polyvalent metal ion water soluble salt and cross-linked polymer is
0.1,0.2,0.3,0.4 etc..
Wherein, in the embodiment of the present invention, when specific implementation, carbon nanotube can be single-walled nanotube, double-walled carbon nano-tube,
Any one in multi-walled carbon nanotube and beamforming carbon nanotube or a variety of combinations, wherein excellent in the embodiment of the present invention
Choosing is using the diameter with 5-50nm and the carbon nanotube of 30-100 μm of length.
When specific implementation, the lamella of the graphene of the embodiment of the present invention can be single layer and/or 2-8 layers.
Wherein, above-mentioned conductive aqueous binders provided in an embodiment of the present invention, viscosity 200-20000mPa.s, preferably
Viscosity is 500-8000mPa.s, and more preferable viscosity is 800-5000mPa.s.
The binder that the above embodiment of the present invention provides can be not only used for conventional carbons negative electrode active material, such as artificial
Graphite, natural graphite, composite graphite, electrically conductive graphite, soft carbon, hard carbon class active material, it can also be used to can be realized high capacity
Negative electrode active material, such as the electrode of the lithium ion battery of silicon class, tin class or silico-carbo class active material.Due to cross-linked polymer quilt
It being chemically bonded on graphene and carbon nanotube, binder thus improves the dispersion of graphene and carbon nanotube, simultaneously as
Sodium alginate and/or potassium alginate itself have different location on helical structure, graphene and carbon nanotube and cross-linked polymer
Group bonding so which form three-dimensional conductive structure, due to foring three-dimensional conductive access with low amounts, when driving lithium from
Due to being charged and discharged in the expansion and contraction process that cause active material when sub- battery, due to being increased by three-dimensional conductive network
The tensile strength of binder maintains conduction path, and binder thus improves expansion and the lithium ion battery of active material
Service life.
The embodiment of the present invention further provides for a kind of preparation method of conductive aqueous binders, referring to Fig. 1, Fig. 1 is this
The flow chart of the preparation method for the conductive aqueous binders that inventive embodiments provide, as shown, the conduction of the embodiment of the present invention
The preparation methods of aqueous binders the following steps are included:
S101: the graphene and carbon nanotube with functional group are added into cross-linked polymer, is mixed to form conducting polymer
Object.
Wherein, functional group is one or more of carboxyl, hydroxyl and chlorine acyl group, in order to be formed and polymer-bound
Chemical bond, graphene and carbon nanotube be added before polymer, need first to graphene and carbon nanotube pre-processed with
Carboxyl, hydroxyl or acid chloride group are introduced on graphene and carbon nanotube.Strong oxidizing property strong acid treatment or logical can be used for example
Crossing the mixed gas with oxidation effectiveness contains graphene and carbon nano tube surface in carboxyl and hydroxyl through high-temperature process
It is one or two kinds of.In order to enable to generate chemical bond between graphene and carbon nanotube and polymer, it can further pass through it
His chemical modification mode, such as acid processing, catalyst treatment, are modified the graphene containing carboxyl and carbon nanotube, and
Chemical bonding occurs with polymer to react.As one of concrete implementation mode, wherein graphene and carbon nanotube are through locating
After reason makes its surface contain carboxyl and hydroxyorgano group, then carboxyl is set to be modified as chlorine acyl under thionyl chloride effect
Base.Certainly, after such modification, the surface of carbon nanotube and graphene may be containing carboxyl, hydroxyl or chlorine acyl group
In one of which, it is also possible to containing two kinds or three kinds in carboxyl, hydroxyl and chlorine acyl group, such as part carboxyl quilt
It is modified as chlorine acyl group, or whole carboxyls are modified as chlorine acyl group etc..
Wherein, cross-linked polymer is sodium alginate and one of which or two kinds of combination in potassium alginate.
Wherein, in the embodiment of the present invention, when specific implementation, carbon nanotube can be single-walled nanotube, double-walled carbon nano-tube,
Any one in multi-walled carbon nanotube and beamforming carbon nanotube or a variety of combinations, wherein excellent in the embodiment of the present invention
Choosing is using the diameter with 5-50nm and the carbon nanotube of 30-100 μm of length.
When specific implementation, the lamella of the graphene of the embodiment of the present invention can be single layer and/or 2-8 layers.
S102: being added polyvalent metal ion salting liquid into conducting polymer, stirring crosslinking react to be formed it is conductive aqueous viscous
Tie agent.
Wherein, as an example, polyvalent metal ion water-soluble salt solution can be Ca2+、Al3+、Ba2+、Zn2+、Fe3+、Cu2+
One of or a variety of combination in water soluble salt.Wherein, it is preferred to use Ca2+Water soluble salt.
Wherein, implementation as one preferred, in conductive aqueous binders, the mass percent of cross-linked polymer
Content is 5%-50%, such as 10%, 15%, 20%, 25%, 40%, 45% etc., the mass percentage content of graphene is
0.1%-5%, such as 0.3%, 0.5%, 1%, 3%, 4% etc., the mass percentage content of carbon nanotube is 0.3%-
15%, such as 0.5%, 1.5%, 2%, 5%, 8%, 10%, 12% etc., the quality of polyvalent metal ion water soluble salt and poly-
The ratio for closing amount of substance is a, 0 < a < 0.5.For example the mass ratio of polyvalent metal ion water soluble salt and cross-linked polymer is
0.1,0.2,0.3,0.4 etc..
The preparation method of the embodiment of the present invention, when cross-linked polymer is formed with graphene and carbon nanotube by bonding action
After conducting polymer, during preparing slurry, polyvalent metal ion water soluble salt is added, conducting polymer will starched
It is cross-linked in situ in material, forms three-dimensional coherent network frame structure, the formation of the three-dimensional structure both can be in active material particle
Between, good three-dimensional adhesiving effect is formed between active material and collector, while three-dimensional conductive network can also be locked
It is scheduled in frame structure, therefore three-dimensional conductive network increases the tensile strength of binder, three-dimensional coherent network is evenly dispersed
Graphene and carbon nanotube, form the transport properties of face and line, and the two interaction forms two three-dimensional integrated bondings
And conductive network.
Graphene and carbon nanotube and sodium alginate and/or potassium alginate are chemically bonded, and can be ionic bond bonding or total
Covalent bond, therefore not only by there is an ion key connection between graphene and carbon nanotube and polymer, and reality from
Sub-key close during there are also covalently key connection, thus graphene and carbon nanotube are not in reunite and can be in dispersion process
Reach good dispersion effect.
The conductive aqueous binders and preparation method thereof that the above embodiment of the present invention provides, three-dimensional conductive provided by the invention
For network aqueous binders tool there are two types of integrated three-dimensional net structure, one kind is polymer and polyvalent metal ion water soluble salt
Three-dimensional coherent network made of solution crosslinking, it is a kind of to be bonded with the cross-linked polymer graphene and carbon nanotube composition
Three-dimensional conductive network.Three-dimensional coherent network provides integrated rigid network architecture in cathode pole piece, ensures active matter
Between matter particle, adhesiveness between active material and collector improves bulking effect of the pole piece in charge and discharge process.It is three-dimensional
Conductive structure provides three-dimensional conductive network structure in cathode pole piece, and the contact between active material particle can be significantly reduced
Polarization in internal resistance and charge and discharge process improves whole conductivity, improves battery long circulating and high rate performance.
Wherein, the conductive aqueous binders of the embodiment of the present invention, are acted on by chemical bonding, compare physical mixed, can be with
The reunion of graphene and carbon nanotube in dispersion process is substantially eliminated, is uniformly divided so that two-dimensional graphene and one-dimensional carbon pipe are formed
The three-dimensional conductive network structure of cloth both with the electronics conduction on face in the structure, while can make anode active material particles
Between realize long range electronics conduction.In addition, can effectively promote mixing efficiency, mistake after by the way that the binder is added
It does not need that conductive agent is added again in journey.
The embodiment of the present invention prepares conductive aqueous binders, and in slurry preparation process, it is water-soluble that polyvalent metal ion is added
Property salting liquid, be cross-linked in situ to form stereoscopic three-dimensional network structure, the network structure have good rigid frame structure, can will
Anode active material particles closely fetter, the effective bulking effect for improving pole piece in charge and discharge process, especially for silicon
Base, tin-based material significant effect.
On the basis of above conductive aqueous binders provided by the invention and preparation method thereof, the embodiment of the present invention is into one
Step provides a kind of lithium ion battery, and the lithium ion battery is by lithium-ion negative pole pole piece, anode pole piece, diaphragm, electrolyte and outer
Shell composition, wherein lithium ion battery negative electrode is the above-mentioned conductive aqueous binders and negative electrode active by the embodiment of the present invention
The slurry of material mixing configuration is coated and dries to be formed.
Wherein, during preparing lithium ion battery negative electrode, the crosslinking of polymer is sent out in negative electrode slurry preparation process
Life is parallel at three-dimensional coherent network.For example, silicon carbon material and the conduction aqueous binders are added after mixing suitable more
Valence metal ion salt, such as calcium chloride, high-speed stirred slurry, polymer are cross-linked in situ reaction, form inside and lead with three-dimensional
The negative electrode slurry of electricity and three-dimensional coherent network structure.
Wherein, negative electrode active material, positive active material used in the lithium ion battery of the embodiment of the present invention, conductive agent,
Diaphragm, electrolyte etc. are all the common materials of traditional lithium-ion battery, and negative electrode active material includes silicon substrate, tin-based material, preparation
The method of lithium ion battery is also the preparation method of traditional lithium-ion battery, the embodiment of the present invention to lithium ion battery other often
The preparation details of gauge material and specific lithium ion battery repeats no more.
Technical solution in order to further illustrate the present invention, is illustrated below by way of specific embodiment, following institute
Stating embodiment is that the representative are limit an embodiment, specific substance, the formula rate being previously mentioned cited by the present invention
And the concrete embodiment of the reaction condition only above-mentioned substance being previously mentioned, formula rate and reaction condition of the invention, and
Not to limit the scope of the invention.
Preparation example 1: the preparation of surface modified graphite alkene and carbon nanotube
(1) preparation of the graphene containing carboxyl:
10g graphite powder, 4.0-4.5g sodium nitrate and the 220-250ml concentrated sulfuric acid are added in glass stirring container, in 0-10
30-40 minutes progress pre-oxidation treatments are stirred at DEG C.After pre-oxidation treatment, by the KMnO of 30g4It is slowly added into, is stirred at room temperature
After 150 minutes, it is slowly added into 50ml deionized water into brown slurry, continues stirring and is added in backward mixture for 120 minutes
The hydrogen peroxide of 1000ml35 DEG C of deionized water and 100ml 30% is centrifuged after mixing evenly, filters.The sample obtained after filtering is first
Cleaned twice with dilute hydrochloric acid, then cleaned 3-5 times repeatedly with deionized water, 80 DEG C of vacuum ovens for 24 hours, obtain table
Contain the graphene powder (raw material A) of carboxyl in face.
(2) carboxyl is introduced in carbon nano tube surface
3g carbon nanotube is pre-processed for 24 hours in 40-50 DEG C of water-bath with the dilute nitric acid solution of 500ml, then spend from
The sub- cleaned carbon nanotube of water.Pretreated carbon nanotube is then added to concentrated nitric acid and the concentrated sulfuric acid (1:3)
In mixture, it is ultrasonically treated the water-bath high speed stirring 8h that 5h is placed on 60-70 DEG C at room temperature, deionized water is used in centrifugation, filtering
Cleaned carbon nanotube 4-5 times obtains the carbon nanotube that surface introduces carboxyl in 80 DEG C of vacuum ovens for 24 hours
(raw material B).
(3) graphene and carbon nano tube surface is carboxy-modified:
A, 0.4g raw material A and 1.2g raw material B are added to the anhydrous tetrahydrofuran solution that 600ml contains 35g thionyl chloride
In, with centrifugation, filtering after being stirred at reflux 12 hours under High Purity Nitrogen atmosphere after ultrasonic treatment 20min, and use anhydrous tetrahydro furan
Cleaned solid matter 4-6 times obtains surface carboxyl groups in 80 DEG C of vacuum ovens for 24 hours and is modified as chlorine acyl
The graphene and carbon nanotube (raw material C) of base.
B, 0.1g raw material A is prepared surface carboxyl groups and be modified with 0.8g raw material B according to the method as a preparation example becomes
The graphene and carbon nanotube (raw material D) of chlorine acyl group.
C, 0.5g raw material A is prepared surface carboxyl groups and be modified with 1.0g raw material B according to the method as a preparation example becomes
The graphene and carbon nanotube (raw material E) of chlorine acyl group.
Preparation example 2: the preparation of aqueous binders
A, 2g sodium alginate is mixed with 50g toluene (using as solvent), is placed in 80 DEG C of oil baths, by 0.3g preparation example
1 raw material C was put into reaction vessel, with ultrasonic wave decentralized processing 30 minutes.Then, 0.5ml tri- is added into said mixture
Ethamine (uses) as solvent, and high-speed stirred reaction vessel 24 hours.After the reaction was completed, the mixture in reaction vessel is poured into
200ml ethyl alcohol (uses) as solvent, then binder (raw material F) is obtained by filtering, washing and drying treatment, in the bonding
Graphene and carbon nanotube are covalently attached to sodium alginate in agent.
B, 2g sodium alginate is mixed with the mixture of potassium alginate with 50g toluene (using as solvent), is placed in 80 DEG C
In oil bath, the raw material C of 0.1g preparation example 1 is put into reaction vessel, with ultrasonic wave decentralized processing 30 minutes.Then, to above-mentioned
0.5ml triethylamine (using as solvent) is added in mixture, high-speed stirred reaction vessel 24 hours.It after the reaction was completed, will be anti-
It answers the mixture in container to pour into 200ml ethyl alcohol (using as solvent), is then glued by filtering, washing and drying treatment
It ties agent (raw material G), graphene and carbon nanotube are covalently attached to sodium alginate in the binder.
C, identical preparation method is used with a, the difference is that it is raw material D that graphene and carbon nanotube, which is added, prepared
Binder is raw material H；
D, identical preparation method is used with b, the difference is that it is raw material E that graphene and carbon nanotube, which is added, prepared
Binder is raw material I；
Then raw material F, raw material G, raw material H and raw material I are distributed in the deionized water of different quality, are prepared into solid content
For 10%, 20%, 30%, 50% conductive aqueous binders.
Embodiment 1
The battery size of preparation is 554065P, and battery core uses takeup type, encapsulates to form polymer Soft Roll electricity by aluminum plastic film
Pond；
By the silicon-carbon cathode active material (silicon carbon material gram volume is 500mAh/g) of 97.0wt%, 3.0wt% conductivity water
Property binder (the 30% solid content aqueous binder that raw material F is prepared) is uniformly mixed with deionized water, and conductivity water is then added
Binder is cross-linked in situ to form three-dimensional conductive binder net after high-speed stirred 30min by the calcium nitrate of property weight of binder 30%
Network.Prepared slurry is uniformly coated on 8 μm of copper foils, cathode pole piece is made after toasted, roll-in, soldering polar ear,
Middle cathode pole piece compacting is 1.70g/cm3；
By the cobalt acid lithium of 98.3wt%, the carbon nanotube of 0.5wt%, the polyvinylidene fluoride and N- methyl pyrrole of 1.2wt%
Pyrrolidone is mixed into slurry, is coated uniformly on 16 μm of aluminium foils, and anode pole piece is made after toasted, roll-in, soldering polar ear；
The positive plate prepared, negative electrode tab and diaphragm are formed into battery core in a winding manner, encapsulate to be formed by aluminum plastic film
Soft pack cell injects chemical conversion, partial volume after electrolyte.
After partial volume, battery energy density 800WH/L, 4.35V cathode pole piece is expanded to 16.4%, 1C/1C and recycles 500 weeks
80% or more conservation rate, for cycle battery thickness swelling less than 8%, specific cyclic curve is shown in Fig. 2.
Embodiment 2
The battery size of preparation is 4.0Ah/18650, and battery core uses takeup type, and shell is steel shell encapsulation.
By the silicon-carbon cathode active material (silicon carbon material gram volume is 650mAh/g) of 96.0wt%, 4.0wt% conductivity water
Property binder (the 50% solid content aqueous binder that raw material H is prepared) is uniformly mixed with deionized water, and conductivity water is then added
Binder is cross-linked in situ to form three-dimensional conductive binder net after high-speed stirred 40min by the calcium chloride of property weight of binder 30%
Network.Prepared slurry is uniformly coated on 8 μm of copper foils, cathode pole piece is made after toasted, roll-in, soldering polar ear,
Middle cathode pole piece compacting is 1.70g/cm3；
By the cobalt acid lithium of 97.5wt%, the polyvinylidene fluoride and N-Methyl pyrrolidone of the S-P of 1.0wt%, 1.5wt%
It is mixed into slurry, is coated uniformly on 16 μm of aluminium foils, anode pole piece is made after toasted, roll-in, soldering polar ear；
The positive plate prepared, negative electrode tab and diaphragm are formed into battery core in a winding manner, are packed into cylindrical shell, injection
Electrolyte post package, chemical conversion, partial volume.
Partial volume battery actual capacity is 4030mAh, and 0.3C fills 1C and recycles 500 weeks 80% or more conservation rates, 2C multiplying power discharging
It is the 92.4% of 0.2C discharge capacity.
Embodiment 3
Battery is prepared using battery size and mode same as Example 1, the difference is that by negative electrode active material silicon-carbon
The capacity of material is changed to 600mAh/g, and the binder is changed to raw material I is prepared 20% solid content aqueous binder.
After partial volume, 4.35V cathode pole piece is expanded to 18.9%, 1C/1C and recycles 300 weeks 80% or more conservation rates, circulation electricity
Pond thickness swelling is less than 7%.
Embodiment 4
Battery is prepared using battery size and mode same as Example 2, the difference is that binder used is using former
The 30% solid content aqueous binder that material G is prepared.
Partial volume battery actual capacity is 4018mAh, and 0.3C fills 1C and recycles 500 weeks 80% or more conservation rates, 2C multiplying power discharging
It is the 93.1% of 0.2C discharge capacity.
Comparative example 1
Anode pole piece and battery are prepared by the way of same as Example 1, is not both, and cathode pole piece is in the following way
Production:
By the silicon-carbon cathode active material (silicon carbon material gram volume is 500mAh/g) of 94.5wt%, the S-P of 2.0wt% is led
Electric agent, 1.5wt%CMC and 2.0wt%SBR are mixed into negative electrode slurry.Prepared slurry is uniformly coated in 8 μm of copper foils
On, cathode pole piece is made after toasted, roll-in, soldering polar ear, wherein cathode pole piece compacting is 1.70g/cm3；
After partial volume, battery energy density 700WH/L, 4.35V cathode pole piece is expanded to 21.4%, 1C/1C and recycles 200 weeks
Conservation rate 80%, cycle battery thickness swelling 8.6%, specific cyclic curve are shown in Fig. 1.Compared to embodiment 1, cathode pole piece expansion is bright
Aobvious to increase, cycle performance is obviously deteriorated, show the three-dimensional conductive aqueous binders use can improve silicon-carbon material significantly
Expect expansion and cycle performance on high-capacity battery.
Comparative example 2
Anode pole piece and battery are prepared by the way of same as Example 1, is not both, and cathode pole piece is in the following way
Production:
By the silicon-carbon cathode active material (silicon carbon material gram volume is 500mAh/g) of 95.5wt%, the raw material A of 0.5wt%
With 1.0% raw material B, 3.0% sodium alginate after mixing, be added aqueous binders weight 25% calcium chloride, high speed
Binder is cross-linked in situ after stirring 30min.Prepared slurry is uniformly coated on 8 μm of copper foils, toasted, roll-in,
Cathode pole piece is made after soldering polar ear, wherein cathode pole piece compacting is 1.70g/cm3；
After partial volume, battery energy density 750WH/L, 4.35V cathode pole piece is expanded to 20.4%, 1C/1C and recycles 300 weeks
Conservation rate 80%, cycle battery thickness swelling 7.6%.
Comparative example 3
Anode pole piece and battery are prepared by the way of same as Example 2, is not both, and cathode pole piece is in the following way
Production:
By the silicon-carbon cathode active material (silicon carbon material gram volume is 650mAh/g) of 94.0wt%, the S-P of 2.0wt% is led
Electric agent, 4.0wt% sodium alginate are uniformly mixed with deionized water, and the chlorination of conductive aqueous weight of binder 15% is then added
Binder is cross-linked in situ to form three-dimensional binder network after high-speed stirred 40min by calcium.Prepared slurry is uniformly coated
On 8 μm of copper foils, cathode pole piece is made after toasted, roll-in, soldering polar ear, wherein cathode pole piece compacting is 1.70g/cm3；
After partial volume, battery capacity 3840mAh, 0.3C fill 1C and recycle 300 weeks 80% or more conservation rates, and 2C multiplying power discharging is
The 65.4% of 0.2C discharge capacity, compares embodiment 2, and the circulation and high rate performance of battery are obviously deteriorated.
Detailed process equipment and process flow of the invention that the present invention is explained by the above embodiments, but the present invention is not
It is confined to above-mentioned detailed process equipment and process flow, that is, does not mean that the present invention must rely on above-mentioned detailed process equipment and work
Skill process could be implemented.It should be clear to those skilled in the art, any improvement in the present invention, to product of the present invention
The equivalence replacement of each raw material and addition, the selection of concrete mode of auxiliary element etc., all fall within protection scope of the present invention and public affairs
Within the scope of opening.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification and accompanying drawing content is applied directly or indirectly in other relevant skills
Art field, is included within the scope of the present invention.
Claims (9)
1. a kind of conduction aqueous binders, which is characterized in that the conduction aqueous binders include graphene, carbon nanotube, friendship
Linked polymer and polyvalent metal ion water-soluble salt solution, wherein the graphene and the carbon nanotube respectively with it is described
Cross-linked polymer forms three-dimensional conductive network structure, the cross-linked polymer and the polyvalent metal ion by chemical bonding
Water-soluble salt solution is cross-linked to form three-dimensional coherent network structure；
Wherein, in the conductive aqueous binders, the mass percentage content of the cross-linked polymer is 5-50%, the graphite
The mass percentage content of alkene is 0.1-5%, and the carbon nanotube mass degree is 0.3-15%, the polyvalent metal
Water insoluble nonionic salt and the cross-linked polymer mass ratio are a, wherein 0 < a < 0.5.
2. conduction aqueous binders according to claim 1, which is characterized in that the graphene and the carbon nanotube are
Contain the graphene and carbon nanotube of at least one of hydroxyl, carboxyl and chlorine acyl group in surface；The cross-linked polymer is sea
At least one of mosanom and potassium alginate；The polyvalent metal ion water-soluble salt solution is Ca2+、Al3+、Ba2+、Zn2 +、Fe3+、Cu2+At least one of water-soluble salt solution.
3. conduction aqueous binders according to claim 1, which is characterized in that the carbon nanotube is single
At least one of pipe, double-walled carbon nano-tube, multi-walled carbon nanotube and beamforming carbon nanotube；Wherein, the carbon nanotube tool
There are the diameter of 5-50nm and 30-100 μm of length；The lamella of the graphene is single layer and/or 2-8 layers.
4. it is according to claim 1 conduction aqueous binders, which is characterized in that it is described conduction aqueous binders viscosity be
200-20000mPa.s。
5. a kind of preparation method of conduction aqueous binders, which is characterized in that the described method includes:
The graphene and carbon nanotube with functional group are added into cross-linked polymer, is mixed to form conducting polymer, so that
The graphene and the carbon nanotube form three-dimensional conductive network knot by chemical bonding with the cross-linked polymer respectively
Structure；
Polyvalent metal ion water-soluble salt solution is added into the conducting polymer, stirring crosslinking is reacted so that the crosslinking
Polymer and the polyvalent metal ion water-soluble salt solution are cross-linked to form three-dimensional coherent network structure, and then form the conduction
Aqueous binders；
Wherein, in the conductive aqueous binders of formation, the mass percentage content of the cross-linked polymer is 5-50%, institute
The mass percentage content for stating graphene is 0.1-5%, and the carbon nanotube mass degree is 0.3-15%, described more
Valence metal ion water soluble salt and the cross-linked polymer mass ratio are a, wherein 0 < a < 0.5.
6. preparation method according to claim 5, which is characterized in that described be added into cross-linked polymer has functional group
Graphene and carbon nanotube, be mixed to form before conducting polymer, further includes:
Surface preparation is carried out to the graphene and the carbon nanotube, contains the graphene and the carbon nano tube surface
There are carboxyl and hydroxyl, then so that the carboxyl is modified as chlorine acyl group by thionyl chloride effect, to have described in being formed
The graphene and carbon nanotube of functional group.
7. preparation method according to claim 5, which is characterized in that the cross-linked polymer is sodium alginate and seaweed
At least one of sour potassium；The polyvalent metal ion water-soluble salt solution is Ca2+、Al3+、Ba2+、Zn2+、Fe3+、Cu2+It is water-soluble
At least one of property salting liquid.
8. a kind of lithium ion battery, which is characterized in that the lithium ion battery by lithium ion battery negative electrode, anode pole piece,
Diaphragm, electrolyte and shell composition, wherein the lithium ion battery negative electrode is as described in claim any one of 1-4
Conductive aqueous binders and negative electrode active material mixed configuration slurry it is coated and dry to be formed.
9. lithium ion battery according to claim 8, which is characterized in that in the slurry, the conduction aqueous binders
Quality be the slurry solids gross mass 0.5-10%.
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Effective date of registration: 20231122 Address after: A2001, Building 1, Beiteri Science and Technology Park, No. 26 Baolan Road, Laokeng Community, Longtian Street, Pingshan District, Shenzhen City, Guangdong Province, 518000 Patentee after: Shenzhen beiteri New Energy Technology Research Institute Co.,Ltd. Address before: 518107 Xitian Community Hi-tech Industrial Park, Gongming Office, Guangming New District, Shenzhen City, Guangdong Province Patentee before: Beitrei New Materials Group Co.,Ltd. |