CN105489898A - Conductive waterborne binder and preparation method therefor, and lithium ion battery - Google Patents
Conductive waterborne binder and preparation method therefor, and lithium ion battery Download PDFInfo
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- CN105489898A CN105489898A CN201511032994.6A CN201511032994A CN105489898A CN 105489898 A CN105489898 A CN 105489898A CN 201511032994 A CN201511032994 A CN 201511032994A CN 105489898 A CN105489898 A CN 105489898A
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- carbon nano
- tube
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- aqueous binders
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- 239000011230 binding agent Substances 0.000 title claims abstract description 94
- 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 36
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 151
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 76
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 76
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 67
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 40
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000012266 salt solution Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 32
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000000460 chlorine Substances 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 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 14
- 239000000661 sodium alginate Substances 0.000 claims description 14
- 235000010413 sodium alginate Nutrition 0.000 claims description 14
- 229940005550 sodium alginate Drugs 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 230000001427 coherent effect Effects 0.000 claims description 11
- 239000002322 conducting polymer Substances 0.000 claims description 10
- 229920001940 conductive polymer Polymers 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- 239000000737 potassium alginate Substances 0.000 claims description 9
- 235000010408 potassium alginate Nutrition 0.000 claims description 9
- 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 9
- 239000007773 negative electrode material Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 241000446313 Lamella Species 0.000 claims description 4
- 239000002079 double walled nanotube Substances 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 239000002048 multi walled nanotube Substances 0.000 claims description 4
- 239000002109 single walled nanotube Substances 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000009938 salting Methods 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 30
- 230000008569 process Effects 0.000 description 26
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 239000011149 active material Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 7
- 238000005476 soldering Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000006182 cathode active material Substances 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 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
- 150000001721 carbon Chemical class 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 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
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 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
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000377 silicon dioxide 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
- 238000004804 winding Methods 0.000 description 2
- 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
- 241000168254 Siro Species 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
- 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007385 chemical modification 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
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 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
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010992 reflux Methods 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
- 238000009987 spinning 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 conductive waterborne binder and a preparation method therefor, and a lithium ion battery. The conductive waterborne binder comprises graphene, a carbon nanotube, a cross-linked polymer and a polyvalent metal ion water soluble salt solution, wherein the graphene and the carbon nanotube is bonded with the cross-linked polymer separately through chemical bonds to form a three-dimensional conductive network structure; and the cross-linked polymer is cross linked with the polyvalent metal ion water soluble salt solution to form a three-dimensional bonding network structure. By adoption of the way, the adhesive force of the binder can be effectively improved; and meanwhile, the lithium ion battery can have the advantages of high energy density, long cycling life, rapid charge, and high safety.
Description
Technical field
The present invention relates to field of lithium ion battery, be specifically related to a kind of conduction aqueous binders and preparation method thereof, lithium ion battery.
Background technology
Along with the development of New Energy Industry, lithium ion battery as the new forms of energy of green, environmental protection at digital products, electric tool series products, electric automobile, electric bus, heavy-duty car is widely used, along with the continuous expansion of application, people have higher requirement to the energy density of lithium ion battery and security performance.
Binding agent tool in Modern electrochemistry device is of great significance, although it is not the electro-chemical activity composition of battery, is electrode active material compact siro spinning technology important component together.The mechanical property of binding agent itself and electrochemical stability also have significant impact to the overall performance of battery.What current battery industry was conventional is bonded with two types: one is linear polymeric binding agent, comprise vinylidene (PVDF), sodium carboxymethylcellulose (CMC) etc., operation technique is ripe, the stable performance of binding agent itself, but use this binding agent to prepare electrode slice to need to consume a large amount of 1-METHYLPYRROLIDONE (NMP) organic solvent, price is high, big for environment pollution.Another kind is point type binding agent, as butadiene-styrene rubber (SBR) emulsion, polytetrafluoroethylene (PTFE) emulsion, this kind of binding agent lacks long-range cementing property, there is mechanical performance bad, tensile strength is not high and this self resistance is high, to the long-term cycle performance of battery and high-rate charge-discharge capability unfavorable.
How a kind of combination property of binding agent is provided, makes, while raising binding agent adhesion, to reduce use amount and polarization of electrode internal resistance, extend the useful life of battery, become and have important technological problems to be solved.
Summary of the invention
The technical problem that the present invention mainly solves is to provide a kind of conduction aqueous binders and preparation method thereof, lithium ion battery, effectively can improve the adhesion of binding agent, be applied to lithium ion battery simultaneously, lithium ion battery can be made simultaneously to have high-energy-density, long circulating, fill soon, high security advantage.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: provide a kind of conduction aqueous binders, described conduction aqueous binders comprises Graphene, carbon nano-tube, cross-linked polymer and polyvalent metal ion water-soluble salt solution, wherein, described Graphene and described carbon nano-tube form three-dimensional conductive network configuration with described cross-linked polymer by chemical bonding respectively, and described cross-linked polymer and described polyvalent metal ion water-soluble salt solution are cross-linked to form three-dimensional coherent network structure.
Wherein, described Graphene and described carbon nano-tube are Graphene and the carbon nano-tube that at least one in hydroxyl, carboxyl and chlorine acyl group is contained on surface; Described cross-linked polymer is at least one in sodium alginate and potassium alginate; Described polyvalent metal ion water-soluble salt solution is Ca
2+, Al
3+, Ba
2+, Zn
2+, Fe
3+, Cu
2+at least one in water soluble salt.
Wherein, in described conduction aqueous binders, the mass percentage content of described cross-linked polymer is 5-50%, the mass percentage content of described Graphene is 0.1-5%, described carbon nanotube mass degree is 0.3-15%, described polyvalent metal ion water soluble salt and described cross-linked polymer mass ratio are a, wherein, and 0<a<0.5.
Wherein, described carbon nano-tube is at least one in Single Walled Carbon Nanotube, double-walled carbon nano-tube, multi-walled carbon nano-tubes and beamforming carbon nano-tube; Wherein, described carbon nano-tube has the diameter of 5-50nm and the length of 30-100 μm; The lamella of described Graphene is individual layer and/or 2-8 layer.
Wherein, the viscosity of described conduction aqueous binders is 200-20000mPa.s.
For solving the problems of the technologies described above, another technical solution used in the present invention is: provide a kind of preparation method of conducting electricity aqueous binders, described method comprises: in cross-linked polymer, add the Graphene with functional group and carbon nano-tube, be mixed to form conducting polymer; In described conducting polymer, add polyvalent metal ion salting liquid, stir cross-linking reaction and form described conduction aqueous binders.
Wherein, described functional group is at least one in carboxyl, hydroxyl and chlorine acyl group; describedly in cross-linked polymer, add the Graphene and carbon nano-tube with functional group; before being mixed to form conducting polymer; also comprise: surface preparation is carried out to described Graphene and described carbon nano-tube; described Graphene and described carbon nano tube surface is made to contain carboxyl and hydroxyl; then by thionyl chloride effect, described carboxyl is modified and becomes chlorine acyl group, thus described in being formed, there is Graphene and the carbon nano-tube of functional group.
Wherein, described cross-linked polymer is at least one in sodium alginate and potassium alginate; Described polyvalent metal ion water-soluble salt solution is Ca
2+, Al
3+, Ba
2+, Zn
2+, Fe
3+, Cu
2+at least one in water soluble salt; In described conduction aqueous binders, the mass percentage content of described cross-linked polymer is 5-50%, the mass percentage content of described Graphene is 0.1-5%, described carbon nanotube mass degree is 0.3-15%, described polyvalent metal ion water soluble salt and described cross-linked polymer mass ratio are a, wherein, 0<a<0.5.
For solving the problems of the technologies described above, another technical solution used in the present invention is: provide a kind of lithium ion battery, described lithium ion battery is made up of lithium ion battery negative electrode, anode pole piece, barrier film, electrolyte and shell, wherein, described lithium ion battery negative electrode is that the slurry of conduction aqueous binders described above and negative electrode active material mixed configuration is formed through being coated with and drying.
Wherein, in described slurry, the quality of described conduction aqueous binders is the 0.5-10% of described slurry solids gross mass.
The invention has the beneficial effects as follows: the situation being different from prior art, conduction aqueous binders provided by the invention comprises Graphene, carbon nano-tube, cross-linked polymer and polyvalent metal ion water-soluble salt solution, wherein, Graphene and carbon nano-tube form three-dimensional conductive network configuration with cross-linked polymer by chemical bonding respectively, and cross-linked polymer and polyvalent metal ion water-soluble salt solution are cross-linked to form three-dimensional coherent network structure.Conduction aqueous binders of the present invention is applied to lithium ion battery, by three-dimensional coherent network structure and the acting in conjunction of three-dimensional conductive network configuration of binding agent, effectively can improves cell integrated conductance and improve battery long circulating and high rate performance.
Accompanying drawing explanation
The flow chart of a kind of preparation method of conducting electricity aqueous binders that Fig. 1 is that the embodiment of the present invention provides;
The lithium ion battery circulation comparison diagram that Fig. 2 is the embodiment of the present invention 1, embodiment 2 obtains with comparative example 1.
Embodiment
Below, in conjunction with specific embodiments and accompanying drawing the present invention is described in detail, it should be noted that, the concrete material mentioned in the following embodiment of the present invention, just be described, not as limit, namely under the same terms as one citing, can also substitute with other materials that concrete material cited in the embodiment of the present invention is similar and realize technical scheme of the present invention, the present invention does not illustrate one by one.Those skilled in the art, when not needing to pay creative work, adopt material other materials that are similar or similar listed by the embodiment of the present invention to realize the present invention, also belong to the scope of protection of the invention.
The embodiment of the present invention provides a kind of conduction aqueous binders, this conduction aqueous binders comprises Graphene, carbon nano-tube, cross-linked polymer and polyvalent metal ion water-soluble salt solution, wherein, the conduction aqueous binders of the embodiment of the present invention has three-dimensional net structure, wherein, the three-dimensional coherent network structure that is cross-linked by polymer and polyvalent metal ion water-soluble salt solution of three-dimensional net structure and forming with the three-dimensional conductive network that Graphene and the carbon nano-tube of polymer-bound form.
Wherein, as the preferred implementation of one, Graphene is preferably surface containing one or more the Graphene in hydroxyl, carboxyl and chloramines base, and carbon nano-tube is preferably surface containing one or more the carbon nano-tube in hydroxyl, carboxyl and chloramines base.Can in preparation process, Graphene and carbon nano-tube make its surface containing carboxyl, hydroxyorgano group by strong oxidizing property strong acid treatment or by the mist with oxidation effectiveness through high-temperature process before the use.
Wherein, as one citing, the cross-linked polymer of the embodiment of the present invention can be the combination of wherein a kind of in sodium alginate and potassium alginate or two kinds, and polyvalent metal ion water-soluble salt solution is Ca
2+, Al
3+, Ba
2+, Zn
2+, Fe
3+, Cu
2+wherein one or more combination in water soluble salt.Wherein, preferably Ca is adopted
2+water soluble salt.
Wherein, as the preferred implementation of one, in conduction aqueous binders, the mass percentage content of cross-linked polymer 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 nano-tube 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 the ratio of polymer quality are a, 0 < a < 0.5.The mass ratio of such as 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, during specific implementation, carbon nano-tube can be any one or multiple combination in single-walled nanotube, double-walled carbon nano-tube, multi-walled carbon nano-tubes and beamforming carbon nano-tube, wherein, in the embodiment of the present invention, preferably adopt the carbon nano-tube with the diameter of 5-50nm and the length of 30-100 μm.
During specific implementation, the lamella of the Graphene of the embodiment of the present invention can be individual layer, and/or 2-8 layer.
Wherein, the above-mentioned conduction aqueous binders that the embodiment of the present invention provides, its viscosity is 200-20000mPa.s, and preferred viscosities is 500-8000mPa.s, and more preferably viscosity is 800-5000mPa.s.
The binding agent that the above embodiment of the present invention provides not only may be used for conventional carbon class negative electrode active material, as Delanium, native graphite, composite graphite, electrically conductive graphite, soft carbon, hard carbon class active material, also can be used for the negative electrode active material that can realize high power capacity, as the electrode of the lithium ion battery of silicon class, tin class or silico-carbo class active material.Because cross-linked polymer is chemically bonded in Graphene and carbon nano-tube, thus binding agent improves the dispersion of Graphene and carbon nano-tube, simultaneously, because sodium alginate and/or potassium alginate itself have helical structure, the group bonding of diverse location on Graphene and carbon nano-tube and cross-linked polymer, make to which form three-dimensional conductive structure, owing to defining three-dimensional conductive path with low amounts, in the expansion causing active material due to charging and discharging when driving lithium ion battery and contraction process, because the tensile strength being added binding agent by three-dimensional conductive network maintains conduction path, thus binding agent improves the expansion of active material and the life-span of lithium ion battery.
The embodiment of the present invention provides a kind of preparation method of conducting electricity aqueous binders further, refer to Fig. 1, Fig. 1 is the flow chart of the preparation method of the conduction aqueous binders that the embodiment of the present invention provides, and as shown in the figure, the preparation method of the conduction aqueous binders of the embodiment of the present invention comprises the following steps:
S101: add the Graphene with functional group and carbon nano-tube in cross-linked polymer, be mixed to form conducting polymer.
Wherein, functional group is one or more in carboxyl, hydroxyl and chlorine acyl group; in order to form the chemical bond with polymer-bound; before Graphene and carbon nano-tube add polymer, need first to carry out preliminary treatment to introduce carboxyl, hydroxyl or acid chloride group on Graphene and carbon nano-tube to Graphene and carbon nano-tube.Such as can use strong oxidizing property strong acid treatment or make Graphene and carbon nano tube surface contain one in carboxyl and hydroxyl or two kinds by the mist with oxidation effectiveness through high-temperature process.In order to make Graphene and produce chemical bond between carbon nano-tube energy and polymer, can further by other chemical modification mode, as acid treatment, catalyst treatment, modification is carried out to the Graphene containing carboxyl and carbon nano-tube, and react with polymer generation chemical bonding.As wherein a kind of concrete implementation, wherein Graphene and treated its surface that makes of carbon nano-tube are containing after carboxyl and hydroxyorgano group, and under thionyl chloride effect, carboxyl being modified subsequently becomes chlorine acyl group.Certainly; after such modification; the surface of carbon nano-tube and Graphene may be containing the wherein one in carboxyl, hydroxyl or chlorine acyl group; also may be containing two kinds in carboxyl, hydroxyl and chlorine acyl group or three kinds; such as a part carboxyl is modified as chlorine acyl group, or all carboxyl is modified as chlorine acyl group etc.
Wherein, cross-linked polymer is the combination of wherein a kind of in sodium alginate and potassium alginate or two kinds.
Wherein, in the embodiment of the present invention, during specific implementation, carbon nano-tube can be any one or multiple combination in single-walled nanotube, double-walled carbon nano-tube, multi-walled carbon nano-tubes and beamforming carbon nano-tube, wherein, in the embodiment of the present invention, preferably adopt the carbon nano-tube with the diameter of 5-50nm and the length of 30-100 μm.
During specific implementation, the lamella of the Graphene of the embodiment of the present invention can be individual layer, and/or 2-8 layer.
S102: add polyvalent metal ion salting liquid in conducting polymer, stirs cross-linking reaction and forms conduction aqueous binders.
Wherein, as an example, polyvalent metal ion water-soluble salt solution can be Ca
2+, Al
3+, Ba
2+, Zn
2+, Fe
3+, Cu
2+wherein one or more combination in water soluble salt.Wherein, preferably Ca is adopted
2+water soluble salt.
Wherein, as the preferred implementation of one, in conduction aqueous binders, the mass percentage content of cross-linked polymer 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 nano-tube 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 the ratio of polymer quality are a, 0 < a < 0.5.The mass ratio of such as 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, after cross-linked polymer and Graphene and carbon nano-tube form conducting polymer by bonding action, in the process preparing slurry, add polyvalent metal ion water soluble salt, conducting polymer will be in-situ cross-linked in the slurry, form three-dimensional coherent network frame structure, the formation of this three-dimensional structure, both can between active material particle, good three-dimensional adhesiving effect is formed between active material and collector, also can the conductive network of three-dimensional be locked in frame structure simultaneously, therefore three-dimensional conductive network adds the tensile strength of binding agent, three-dimensional coherent network is dispersed Graphene and carbon nano-tube, define the transport properties of face and line, both interact, define two three-dimensional integrated bondings and conductive network.
Graphene and carbon nano-tube and sodium alginate and/or potassium alginate chemical bonding, can be ionic bond bonding or covalent bonding, therefore Graphene and between carbon nano-tube with polymer not only by there being ionic bond to be connected, and in actual ions bonding process, also have covalent bond to connect, thus Graphene and carbon nano-tube there will not be reunion and can reach good dispersion effect in dispersion process.
Conduction aqueous binders that the above embodiment of the present invention provides and preparation method thereof, three-dimensional conductive network aqueous binders provided by the invention has two kinds of integrated three-dimensional net structures, for the three-dimensional coherent network that polymer and polyvalent metal ion water-soluble salt solution are cross-linked, a kind of is the three-dimensional conductive network formed with the Graphene of described cross-linked polymer bonding and carbon nano-tube.Three-dimensional coherent network provides the rigidity network architecture of integration in cathode pole piece, ensures that between active material particle, the adhesiveness between active material and collector, improves the bulking effect of pole piece in charge and discharge process.Three-dimensional conductive structure provides three-dimensional conductive network structure in cathode pole piece, significantly can reduce the contact internal resistance between active material particle and the polarization in charge and discharge process, improves whole conductivity, improves battery long circulating and high rate performance.
Wherein, the conduction aqueous binders of the embodiment of the present invention, by chemical bonding effect, compare physical mixed, significantly can eliminate Graphene and the reunion of carbon nano-tube in dispersion process, make two-dimensional graphene and the tubular three-dimensional conductive network configuration uniformly distributed of one dimension carbon, both there is in this structure the electrical conductivity on face, the electrical conductivity realizing long distance between anode active material particles can be made simultaneously.In addition, after adding this binding agent, can effectively promote batch mixing efficiency, not need in process again to add conductive agent.
Embodiment of the present invention preparation conduction aqueous binders, in slurry preparation process, add polyvalent metal ion water-soluble salt solution, in-situ cross-linked formation stereoscopic three-dimensional network configuration, this network configuration has good rigid frame structure, anode active material particles closely can be fettered, effectively improve the bulking effect of pole piece in charge and discharge process, especially for silica-based, tin-based material Be very effective.
On the basis of above conduction aqueous binders provided by the invention and preparation method thereof, the embodiment of the present invention provides a kind of lithium ion battery further, this lithium ion battery is made up of lithium-ion negative pole pole piece, anode pole piece, barrier film, electrolyte and shell, wherein, lithium ion battery negative electrode is formed through being coated with and drying by the above-mentioned conduction aqueous binders of the embodiment of the present invention and the slurry of negative electrode active material mixed configuration.
Wherein, prepare in lithium ion battery negative electrode process, being cross-linked of polymer walks abreast into three-dimensional coherent network in cathode size preparation process.Such as, appropriate polyvalent metal ion salt is added after silicon carbon material being mixed with this conduction aqueous binders, as calcium chloride, high-speed stirred slurry, there is in-situ cross-linked reaction in polymer, forms the inner cathode size with three-dimensional conductive and three-dimensional coherent network structure.
Wherein, the lithium ion battery of embodiment of the present invention negative electrode active material, positive active material, conductive agent, barrier film, electrolyte etc. used is all the conventional material of traditional lithium-ion battery, negative electrode active material comprises silica-based, tin-based material, the method preparing lithium ion battery is also the preparation method of traditional lithium-ion battery, and the preparation details of the embodiment of the present invention to other conventional materials of lithium ion battery and concrete lithium ion battery repeats no more.
In order to further illustrate technical scheme of the present invention; be illustrated below by way of specific embodiment; the following stated embodiment is limited the representative embodiment cited by the present invention; the imbody of concrete material, formula rate and the reaction condition mentioned material, formula rate and reaction condition that only the present invention is above-mentioned mentioned, not in order to limit the scope of the invention.
Preparation example 1: the preparation of surface modified graphite alkene and carbon nano-tube
(1) containing the preparation of carboxyl Graphene:
10g graphite powder, 4.0-4.5g sodium nitrate and the 220-250ml concentrated sulfuric acid are added in glass stirred vessel, stir at 0-10 DEG C and carry out pre-oxidation treatment in 30-40 minute.After pre-oxidation treatment, by the KMnO of 30g
4slowly add, after stirring at room temperature 150 minutes, in brown slurry, slowly add 50ml deionized water, continue stirring adds 1000ml35 DEG C of deionized water and 100ml30% for 120 minutes hydrogen peroxide in backward mixture, centrifugal after stirring, filter.The sample obtained after filtering first with watery hydrochloric acid cleaning twice, then cleans 3-5 time with deionized water repeatedly, at the vacuum oven 24h of 80 DEG C, obtains the graphene powder (raw material A) of surface containing carboxyl.
(2) carboxyl is introduced in carbon nano tube surface
By the dilute nitric acid solution of 3g carbon nano-tube 500ml preliminary treatment 24h in the water-bath of 40-50 DEG C, subsequently by the carbon nano-tube after washed with de-ionized water process.Subsequently pretreated carbon nano-tube is joined in the mixture of red fuming nitric acid (RFNA) and the concentrated sulfuric acid (1:3), under room temperature, ultrasonic process 5h is placed on the water-bath high speed stirring 8h of 60-70 DEG C, centrifugal, filtration, by the carbon nano-tube after washed with de-ionized water process 4-5 time, obtain at the vacuum oven 24h of 80 DEG C the carbon nano-tube (raw material B) that carboxyl is introduced on surface.
(3) Graphene and carbon nano tube surface is carboxy-modified:
A, 0.4g raw material A and 1.2g raw material B are joined 600ml contain in the anhydrous tetrahydrofuran solution of 35g thionyl chloride; with after ultrasonic process 20min under High Purity Nitrogen atmosphere stirring and refluxing centrifugal after 12 hours, filter; and with anhydrous tetrahydro furan cleaned solid matter 4-6 time, obtain surface carboxyl groups at the vacuum oven 24h of 80 DEG C and to be modified the Graphene and carbon nano-tube (raw material C) that become chlorine acyl group.
B, 0.1g raw material A and 0.8g raw material B are prepared surface carboxyl groups according to the method that a preparation example is the same to be modified the Graphene and carbon nano-tube (raw material D) that become chlorine acyl group.
C, 0.5g raw material A and 1.0g raw material B are prepared surface carboxyl groups according to the method that a preparation example is the same to be modified the Graphene and carbon nano-tube (raw material E) that become chlorine acyl group.
Preparation example 2: the preparation of aqueous binders
A, 2g sodium alginate to be mixed with 50g toluene (using as solvent), be placed in 80 DEG C of oil baths, the raw material C of 0.3g preparation example 1 is put into reaction vessel, by ultrasonic wave dispersion treatment 30 minutes.Then, in said mixture, 0.5ml triethylamine (using as solvent) is added, high-speed stirred reaction vessel 24 hours.After having reacted, mixture in reaction vessel is poured into 200ml ethanol (using as solvent), then obtain binding agent (raw material F) by filtration, cleaning and dry process, in this binding agent, Graphene and carbon nano-tube are covalently attached to sodium alginate.
B, 2g sodium alginate to be mixed with 50g toluene (using as solvent) with the mixture of potassium alginate, be placed in 80 DEG C of oil baths, the raw material C of 0.1g preparation example 1 is put into reaction vessel, by ultrasonic wave dispersion treatment 30 minutes.Then, in said mixture, 0.5ml triethylamine (using as solvent) is added, high-speed stirred reaction vessel 24 hours.After having reacted, mixture in reaction vessel is poured into 200ml ethanol (using as solvent), then obtain binding agent (raw material G) by filtration, cleaning and dry process, in this binding agent, Graphene and carbon nano-tube are covalently attached to sodium alginate.
C, adopt identical preparation method with a, unlike adding Graphene and carbon nano-tube is raw material D, the binding agent prepared is raw material H;
D, adopt identical preparation method with b, unlike adding Graphene and carbon nano-tube is raw material E, the binding agent prepared 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 the conduction aqueous binders that solid content is 10%, 20%, 30%, 50%.
Embodiment 1
The battery size of preparation is 554065P, and battery core adopts takeup type, forms polymer soft-package battery by aluminum plastic film encapsulation;
By the silicon-carbon cathode active material (silicon carbon material gram volume is 500mAh/g) of 97.0wt%, 3.0wt% conduction aqueous binders (the 30% solid content aqueous binding agent that raw material F prepares) and deionized water Homogeneous phase mixing, add the calcium nitrate of conduction water-based weight of binder 30% subsequently, by in-situ cross-linked for binding agent formation three-dimensional conductive binding agent network after high-speed stirred 30min.Be coated in by prepared slurry on 8 μm of Copper Foils uniformly, obtained cathode pole piece after baking, roll-in, soldering polar ear, wherein cathode pole piece compacting is 1.70g/cm
3;
By the cobalt of 98.3wt% acid lithium, the carbon nano-tube of 0.5wt%, polyvinylidene fluoride and the 1-METHYLPYRROLIDONE of 1.2wt% are mixed into slurry, are evenly coated on 16 μm of aluminium foils, obtained anode pole piece after baking, roll-in, soldering polar ear;
The positive plate prepared, negative plate and barrier film are formed battery core in a winding manner, form soft pack cell by aluminum plastic film encapsulation, inject after electrolyte change into, partial volume.
After partial volume, battery energy density is that 800WH/L, 4.35V cathode pole piece is expanded to 16.4%, 1C/1C and circulates 500 weeks conservation rates more than 80%, and cycle battery thickness swelling is less than 8%, and concrete cyclic curve is shown in Fig. 2.
Embodiment 2
The battery size of preparation is 4.0Ah/18650, and battery core adopts takeup type, and shell is box hat encapsulation.
By the silicon-carbon cathode active material (silicon carbon material gram volume is 650mAh/g) of 96.0wt%, 4.0wt% conduction aqueous binders (the 50% solid content aqueous binding agent that raw material H prepares) and deionized water Homogeneous phase mixing, add the calcium chloride of conduction water-based weight of binder 30% subsequently, by in-situ cross-linked for binding agent formation three-dimensional conductive binding agent network after high-speed stirred 40min.Be coated in by prepared slurry on 8 μm of Copper Foils uniformly, obtained cathode pole piece after baking, roll-in, soldering polar ear, wherein cathode pole piece compacting is 1.70g/cm
3;
By the cobalt of 97.5wt% acid lithium, polyvinylidene fluoride and the 1-METHYLPYRROLIDONE of the S-P of 1.0wt%, 1.5wt% are mixed into slurry, are evenly coated on 16 μm of aluminium foils, obtained anode pole piece after baking, roll-in, soldering polar ear;
The positive plate prepared, negative plate and barrier film are formed battery core in a winding manner, load in barrel shrond, encapsulate after injecting electrolyte, change into, partial volume.
Partial volume battery actual capacity is that to fill 1C 500 weeks conservation rate more than 80%, the 2C multiplying power dischargings that circulate be 92.4% of 0.2C discharge capacity for 4030mAh, 0.3C.
Embodiment 3
Adopt the battery size identical with embodiment 1 and mode to prepare battery, change to 600mAh/g unlike by the capacity of negative electrode active material silicon carbon material, described binding agent changes the 20% solid content aqueous binding agent that raw material I prepares into.
After partial volume, 4.35V cathode pole piece is expanded to 18.9%, 1C/1C and circulates 300 weeks conservation rates more than 80%, and cycle battery thickness swelling is less than 7%.
Embodiment 4
Adopting the battery size identical with embodiment 2 and mode to prepare battery, is the 30% solid content aqueous binding agent adopting raw material G to prepare unlike binding agent used.
Partial volume battery actual capacity is that to fill 1C 500 weeks conservation rate more than 80%, the 2C multiplying power dischargings that circulate be 93.1% of 0.2C discharge capacity for 4018mAh, 0.3C.
Comparative example 1
Adopt the mode identical with embodiment 1 to prepare anode pole piece and battery, be not both, cathode pole piece makes in the following way:
By the silicon-carbon cathode active material (silicon carbon material gram volume is 500mAh/g) of 94.5wt%, the S-P conductive agent of 2.0wt%, 1.5wt%CMC and 2.0wt%SBR is mixed into cathode size.Be coated in by prepared slurry on 8 μm of Copper Foils uniformly, obtained cathode pole piece after baking, roll-in, soldering polar ear, wherein cathode pole piece compacting is 1.70g/cm
3;
After partial volume, battery energy density is that 700WH/L, 4.35V cathode pole piece is expanded to 21.4%, 1C/1C and circulates 200 weeks conservation rates 80%, and cycle battery thickness swelling 8.6%, concrete cyclic curve is shown in Fig. 1.Compare embodiment 1, cathode pole piece expands obviously to be increased, and cycle performance is obviously deteriorated, and what show the use of this three-dimensional conductive aqueous binders can improve the expansion of silicon carbon material on high-capacity battery and cycle performance significantly.
Comparative example 2
Adopt the mode identical with embodiment 1 to prepare anode pole piece and battery, be not both, cathode pole piece makes in the following way:
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% and the raw material B of 1.0%, after the sodium alginate of 3.0% mixes, add the calcium chloride of aqueous binders weight 25%, after high-speed stirred 30min, binding agent is in-situ cross-linked.Be coated in by prepared slurry on 8 μm of Copper Foils uniformly, obtained cathode pole piece after baking, roll-in, soldering polar ear, wherein cathode pole piece compacting is 1.70g/cm
3;
After partial volume, battery energy density is that 750WH/L, 4.35V cathode pole piece is expanded to 20.4%, 1C/1C and circulates 300 weeks conservation rates 80%, cycle battery thickness swelling 7.6%.
Comparative example 3
Adopt the mode identical with embodiment 2 to prepare anode pole piece and battery, be not both, cathode pole piece makes in the following way:
By the silicon-carbon cathode active material (silicon carbon material gram volume is 650mAh/g) of 94.0wt%, the S-P conductive agent of 2.0wt%, 4.0wt% sodium alginate and deionized water Homogeneous phase mixing, add the calcium chloride of conduction water-based weight of binder 15% subsequently, by three-dimensional for in-situ cross-linked for binding agent formation binding agent network after high-speed stirred 40min.Be coated in by prepared slurry on 8 μm of Copper Foils uniformly, obtained cathode pole piece after baking, roll-in, soldering polar ear, wherein cathode pole piece compacting is 1.70g/cm
3;
After partial volume, battery capacity is that to fill 1C 300 weeks conservation rate more than 80%, the 2C multiplying power dischargings that circulate be 65.4% of 0.2C discharge capacity for 3840mAh, 0.3C, and compare embodiment 2, circulation and the high rate performance of battery are obviously deteriorated.
The present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize specification of the present invention and accompanying drawing content to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (10)
1. a conduction aqueous binders, it is characterized in that, described conduction aqueous binders comprises Graphene, carbon nano-tube, cross-linked polymer and polyvalent metal ion water-soluble salt solution, wherein, described Graphene and described carbon nano-tube form three-dimensional conductive network configuration with described cross-linked polymer by chemical bonding respectively, and described cross-linked polymer and described polyvalent metal ion water-soluble salt solution are cross-linked to form three-dimensional coherent network structure.
2. conduction aqueous binders according to claim 1, is characterized in that, described Graphene and described carbon nano-tube are Graphene and the carbon nano-tube that at least one in hydroxyl, carboxyl and chlorine acyl group is contained on surface; Described cross-linked polymer is at least one in sodium alginate and potassium alginate; Described polyvalent metal ion water-soluble salt solution is Ca
2+, Al
3+, Ba
2+, Zn
2+, Fe
3+, Cu
2+at least one in water soluble salt.
3. conduction aqueous binders according to claim 1, it is characterized in that, in described conduction aqueous binders, the mass percentage content of described cross-linked polymer is 5-50%, the mass percentage content of described Graphene is 0.1-5%, and described carbon nanotube mass degree is 0.3-15%, and described polyvalent metal ion water soluble salt and described cross-linked polymer mass ratio are a, wherein, 0<a<0.5.
4. conduction aqueous binders according to claim 1, is characterized in that, described carbon nano-tube is at least one in Single Walled Carbon Nanotube, double-walled carbon nano-tube, multi-walled carbon nano-tubes and beamforming carbon nano-tube; Wherein, described carbon nano-tube has the diameter of 5-50nm and the length of 30-100 μm; The lamella of described Graphene is individual layer and/or 2-8 layer.
5. conduction aqueous binders according to claim 1, is characterized in that, the viscosity of described conduction aqueous binders is 200-20000mPa.s.
6. conduct electricity the preparation method of aqueous binders, it is characterized in that, described method comprises:
In cross-linked polymer, add the Graphene with functional group and carbon nano-tube, be mixed to form conducting polymer;
In described conducting polymer, add polyvalent metal ion salting liquid, stir cross-linking reaction and form described conduction aqueous binders.
7. preparation method according to claim 6; it is characterized in that, described functional group is at least one in carboxyl, hydroxyl and chlorine acyl group, describedly in cross-linked polymer, adds the Graphene and carbon nano-tube with functional group; before being mixed to form conducting polymer, also comprise:
Surface preparation is carried out to described Graphene and described carbon nano-tube; described Graphene and described carbon nano tube surface is made to contain carboxyl and hydroxyl; then by thionyl chloride effect, described carboxyl is modified and becomes chlorine acyl group, thus described in being formed, there is Graphene and the carbon nano-tube of functional group.
8. preparation method according to claim 6, is characterized in that, described cross-linked polymer is at least one in sodium alginate and potassium alginate; Described polyvalent metal ion water-soluble salt solution is Ca
2+, Al
3+, Ba
2+, Zn
2+, Fe
3+, Cu
2+at least one in water soluble salt; In described conduction aqueous binders, the mass percentage content of described cross-linked polymer is 5-50%, the mass percentage content of described Graphene is 0.1-5%, described carbon nanotube mass degree is 0.3-15%, described polyvalent metal ion water soluble salt and described cross-linked polymer mass ratio are a, wherein, 0<a<0.5.
9. a lithium ion battery, it is characterized in that, described lithium ion battery is made up of lithium ion battery negative electrode, anode pole piece, barrier film, electrolyte and shell, wherein, described lithium ion battery negative electrode is formed through being coated with and drying by the slurry of the conduction aqueous binders described in any one of claim 1-5 and negative electrode active material mixed configuration.
10. lithium ion battery according to claim 9, is characterized in that, in described slurry, the quality of described conduction aqueous binders is the 0.5-10% of described slurry solids gross mass.
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| CN110048174A (en) * | 2019-04-29 | 2019-07-23 | 中南大学 | A kind of gel batteries dielectric film and its preparation method and application |
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| CN111809447A (en) * | 2020-05-06 | 2020-10-23 | 为远材料科技(辽宁)有限责任公司 | Conductive paper and preparation method and application thereof |
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