CN114420929B - Preparation method of solid battery containing conductive polymer binder - Google Patents
Preparation method of solid battery containing conductive polymer binder Download PDFInfo
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- CN114420929B CN114420929B CN202111501786.1A CN202111501786A CN114420929B CN 114420929 B CN114420929 B CN 114420929B CN 202111501786 A CN202111501786 A CN 202111501786A CN 114420929 B CN114420929 B CN 114420929B
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- 239000007787 solid Substances 0.000 title claims abstract description 39
- 229920005598 conductive polymer binder Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 15
- 239000011267 electrode slurry Substances 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 23
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 22
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 16
- 239000007784 solid electrolyte Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000010935 stainless steel Substances 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 12
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 11
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011324 bead Substances 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000005543 nano-size silicon particle Substances 0.000 claims description 5
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920004890 Triton X-100 Polymers 0.000 claims description 4
- 239000013504 Triton X-100 Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910004882 Na2S2O8 Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000002203 sulfidic glass Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 abstract description 16
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- 239000011883 electrode binding agent Substances 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010556 emulsion polymerization method Methods 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 239000011884 anode binding agent Substances 0.000 abstract description 2
- 239000006256 anode slurry Substances 0.000 abstract description 2
- 229920005596 polymer binder Polymers 0.000 description 5
- 239000002491 polymer binding agent Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000003232 water-soluble binding agent Substances 0.000 description 3
- 241001391944 Commicarpus scandens Species 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910013391 LizN Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010998 test method 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
- H01M4/622—Binders being polymers
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a solid battery containing a conductive polymer binder, which comprises the following steps: step 1, preparing a water-soluble anode conductive polymer binder and an anode: step 2, preparing a positive electrode containing a conductive polymer binder of the poly PSS: and 3, assembling the solid battery. The invention prepares the aromatic water-soluble conductive polymer by emulsion polymerization method, and prepares the negative electrode slurry by taking the aromatic water-soluble conductive polymer as a silicon-based negative electrode binder; the high-nickel anode slurry is prepared by taking a poly (sodium styrenesulfonate) PSS conductive polymer as an anode binder. By using conductive polymer binder in the anode and the cathode, the electron conductivity of the anode and the cathode is improved, the internal resistance of the solid battery is effectively reduced, and the electrochemical performance of the solid battery is greatly improved.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a preparation method of a solid battery containing a conductive polymer binder.
Background
The lithium secondary battery based on the polymer solid electrolyte can fundamentally solve the safety problem of the liquid lithium ion secondary battery caused by electrolyte leakage, and meanwhile, the energy density of the lithium battery is improved, so that the lithium secondary battery is considered as one of the most promising materials of the solid electrolyte, and the manufacturing of the flaky solid battery electrode by adopting the traditional wet slurry process has great difficulty, and particularly the flaky electrode needs to provide enough mechanical performance by using a polymer adhesive, thereby facilitating production, transportation and battery assembly, buffering the stress and strain generated by chemical machinery during repeated charge and discharge cycles, relieving the formation of cracks, separation of particles and the like. However, the poor chemical stability of the polymer solid electrolyte severely limits the choice of the positive electrode solvent and the binder, and in addition, the high polymer binder blocks poor conductivity at the interface, blocks lithium ion transmission at the interface, and influences the exertion of the electrochemical performance of the battery. Therefore, the optimized high polymer positive electrode binder is used, the comprehensive performance of the solid battery can be improved, and as a special high polymer binder, the conductive high polymer binder shows good application prospect in the field of lithium ion batteries, and the conductive high polymer binder has the advantages of better connection of active materials and reduction of the use amount of conductive additives in the pole piece. Patent application number CN201880089863.7 discloses a battery electrode with a solid polymer electrolyte and a water-soluble binder, the mechanical strength of the pole piece being improved by adding the water-soluble binder to the solid ion-conducting polymer electrolyte.
The water-soluble binder used in the prior art has no electronic conductivity, increases the internal resistance of the solid battery, and is not beneficial to the performance of the battery.
Disclosure of Invention
The present invention is directed to a method for preparing a solid battery containing a conductive polymer binder, which solves the problems set forth in the background art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method for preparing a solid state battery comprising a conductive polymer binder, comprising the steps of:
step 1, preparing a water-soluble anode conductive polymer binder and an anode: firstly, sodium carboxymethylcellulose CMC is dissolved in deionized water, and the mass fraction of CMC is 2-4%; dissolving sodium persulfate Na2S2O8 in proper amount of deionized water, na 2 S 2 O 8 Mixing benzyl methacrylate, CMC solution, polyethylene glycol octyl phenyl ether Triton X-100 and deionized water according to the mass ratio of 10-20:25-35:2-3:70-85, magnetically stirring at normal temperature for 10-30 min to obtain stable emulsion, heating the emulsion to 60-90 ℃ under argon or nitrogen atmosphere, and addingThe method comprises the steps of (1) mixing 1-3% of sodium persulfate solution by mass of the total mixed solution by ultrasonic for 20-40 minutes, continuously dropwise adding benzyl methacrylate and sodium persulfate solution while ultrasonic mixing, respectively adding 12-35% of benzyl methacrylate and 10-25% of sodium persulfate solution by mass of the total mixed solution by mass of the added benzyl methacrylate and sodium persulfate solution, respectively carrying out ultrasonic dispersion on the obtained mixed solution for 1-1.5 hours at 70-85 ℃ and 80-95 ℃ in argon atmosphere or nitrogen atmosphere, and cooling to obtain water-soluble conductive polymer emulsion; silicon nano particles, graphite particles, water-soluble conductive polymer emulsion, carbon conductive agent and deionized water are mixed according to the mass ratio of 30-45:40-45:5-15:1-5:50-70 are added into a high-energy ultrasonic ball mill together, ball milling is carried out for 10-30 minutes at normal temperature, thus obtaining uniformly mixed negative electrode slurry, and the obtained slurry is coated on a negative electrode current collector by a scraper method, thus obtaining a negative electrode plate;
step 2, preparing a positive electrode containing a conductive polymer binder of the poly PSS: dissolving poly PSS in N-methyl pyrrolidone to form a glue solution, wherein the mass fraction of the PSS is 5-10%, adding the glue solution, a high-nickel ternary positive electrode material, lanthanum lithium zirconate LLZO or lanthanum lithium titanate LLTO or titanium aluminum lithium phosphate LATP, and a carbon conductive agent into a high-energy vibration ball mill together, ball milling for 10-30 minutes at normal temperature to obtain a uniformly mixed positive electrode slurry, and coating the positive electrode slurry on a positive electrode current collector to obtain a positive electrode plate;
step 3, assembling a solid battery: and (3) respectively pressing the positive and negative plates prepared in the step (1) and the step (2) on two sides of the solid electrolyte under 200-400 and standard atmospheric pressure, and assembling to obtain the button solid lithium battery.
As a further technical scheme of the invention, the particle size of the silicon nano-particles is 200-800nm.
As a further technical scheme of the invention, the sodium persulfate is replaced by potassium persulfate.
As a further technical scheme of the invention, the ball-material ratio in the step 1 is 1-1.5:1.5-3.0, and the ball-milling beads are zirconium beads.
As a further technical scheme of the invention, the thickness of the negative current collector is 10-50 mu m, the material is one of copper foil, net-shaped copper foil, stainless steel or net-shaped stainless steel, and the coating thickness is 50-250 mu m.
As a further technical scheme of the invention, the thickness of the positive current collector is 10-50 mu m, the material is one of copper foil, net-shaped copper foil, stainless steel or net-shaped stainless steel, and the coating thickness is 50-250 mu m.
As a further aspect of the present invention, the solid electrolyte includes an oxide solid electrolyte, a sulfide solid electrolyte, a polymer solid electrolyte, or any other electrolyte that can be used for a solid lithium battery.
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares the aromatic water-soluble conductive polymer by emulsion polymerization method, and prepares the negative electrode slurry by taking the aromatic water-soluble conductive polymer as a silicon-based negative electrode binder; the high-nickel anode slurry is prepared by taking a poly (sodium styrenesulfonate) PSS conductive polymer as an anode binder. By using conductive polymer binder in the anode and the cathode, the electron conductivity of the anode and the cathode is improved, the internal resistance of the solid battery is effectively reduced, and the electrochemical performance of the solid battery is greatly improved.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
A method for preparing a solid state battery comprising a conductive polymer binder, comprising the steps of:
step 1, a water-soluble negative electrode conductive polymer binder and a negative electrode:
a. the invention adopts emulsion polymerization method to prepare conductive polymer for negative electrode, before preparation, a proper amount of CMC is dissolved in deionized water, and the mass fraction of CMC is 2-4%; sodium persulfate Na 2 S 2 O 8 Dissolving in deionized water, na 2 S 2 O 8 The mass fraction of (2) is 0.1-0.4%. Mixing a certain amount of benzyl methacrylate, CMC solution, polyethylene glycol octyl phenyl ether Triton X-100 and deionized water according to the mass ratio of 10-20:25-35:2-3:70-85, magnetically stirring for 10-30 minutes at normal temperature to obtain a stable emulsion, heating the emulsion to 60-90 ℃ under argon or nitrogen atmosphere, adding sodium persulfate solution, wherein the mass ratio of the sodium persulfate solution to the total mixed solution is 1-3%, carrying out ultrasonic mixing for 20-40 minutes, and continuously dropwise adding the benzyl methacrylate and the sodium persulfate solution while carrying out ultrasonic mixing, wherein the mass ratio of the added benzyl methacrylate and the sodium persulfate solution to the total mixed solution is 12-35% and 10-25%, respectively. And respectively carrying out ultrasonic dispersion on the obtained mixed solution for 1-1.5 hours at 70-85 ℃ and 80-95 ℃ under argon atmosphere or nitrogen atmosphere, and then cooling to finally obtain the water-soluble aromatic negative electrode binder. FIG. 1 shows a synthetic mechanism diagram, in which benzyl methacrylate monomer is a thin liquid and can be directly reacted to form a copolymer emulsion, in addition, highly hydrophilic and lipophilic Triton X-100 and CMC are used as stabilizers to help form a stable colloid system, and sodium persulfate solution is added to improve the water solubility of the system, so that a stable water-soluble conductive polymer emulsion is finally prepared, wherein sodium persulfate can be replaced by potassium persulfate;
the solid content of the prepared polymer emulsion is 15-30%, the manufacturing cost is increased due to the fact that the solid content can be adjusted through water quantity, and the emulsion system is unstable and is easy to subside or delaminate due to the fact that the solid content is too low. The obtained binder emulsion can be used for slurry mixing and electrode coating without further treatment, combines the advantages of a conductive polymer adhesive and an aqueous process, saves energy and time, simultaneously ensures low manufacturing process cost of the negative electrode, and is environment-friendly;
b. silicon nano particles (the particle size is 200-800 nm), graphite particles, water-soluble conductive polymer emulsion, carbon conductive agent and deionized water are mixed according to the mass ratio of 30-45:40-45:5-15:1-5:50-70 of the materials are added into a high-energy ultrasonic ball mill together, the ball-material ratio is 1-1.5:1.5-3.0, the ball-milling beads are zirconium beads, the ball milling is carried out for 10-30 minutes at normal temperature, the uniformly mixed cathode slurry is obtained, and the used carbon conductive agent is one or more of ketjen black, carbon black, conductive graphite, carbon nano tubes or nano carbon fibers. Coating the obtained slurry on a negative current collector by a scraper method, wherein the thickness of the used negative current collector is 10-50 mu m, the thickness of the current collector is too low, the mechanical strength is low, a pole piece is easy to break, the cost is increased due to the too high thickness, the slurry is made of one of copper foil, net-shaped copper foil, stainless steel or net-shaped stainless steel, the coating thickness is 50-250 mu m, the coating thickness is too low, the cost is too high, the adhesion of the pole piece with too high thickness is too low, and the processing performance is poor;
step 2, positive electrode of PSS conductive polymer binder containing poly (sodium styrenesulfonate):
the preparation method comprises the steps of dissolving poly (sodium styrene sulfonate) PSS into a proper amount of N-methylpyrrolidone to form a glue solution, wherein the mass fraction of the PSS is 5-10%, then adding the glue solution, a high-nickel ternary positive electrode material, lanthanum lithium zirconate LLZO or lanthanum lithium titanate LLTO or titanium aluminum lithium phosphate LATP and a carbon conductive agent into a high-energy vibration ball mill together, ball milling for 10-30 minutes at normal temperature to obtain uniformly mixed positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, wherein the thickness of the current collector is 10-50 mu m, the thickness of the current collector is too low in mechanical strength, the pole piece is easy to break, the cost is increased due to the too high thickness, the material is one of aluminum foil, net-shaped aluminum foil, stainless steel or net-shaped stainless steel, the coating thickness is 100-300 mu m, the coating thickness is too low in cost, the adhesive force of the pole piece is too high, and the processing performance is poor.
Step 3, assembling the solid battery:
pressing the prepared positive and negative plates on two sides of solid electrolyte under 200-400 standard atmospheres respectively in argon atmosphere, and assembling to obtain 2032 type button solid lithium battery, wherein the solid electrolyte comprises oxide solid electrolyte (LLZO, LLTO, LATP or LiZn (GeO 4), sulfide solid electrolyte (Li) 2 -S or P 2 S 5 ) Polymer solid electrolytes (polyethylene oxide PEO, etc.) or everything else can be used for the electrolytes of solid lithium batteries.
Example 2, based on example 1, further comprises a test procedure: the direct current resistance of the positive and negative pole pieces is tested at normal temperature by adopting a double-probe method, the direct current resistance mainly reflects the electronic conductivity of the pole pieces, and simultaneously, in order to improve the testing accuracy, the top and the bottom of the pole pieces are respectively sprayed with gold before the testing. And (3) at 30 ℃, in the voltage range of 3.0-4.1V, carrying out charge-discharge cycle at the multiplying power of 0.1-0.3C, and when obvious short circuit occurs (the voltage reduction speed is more than or equal to 5 Mv/S), considering that the service life is ended. The pole piece test results are shown in table 1, and it can be seen that for the silicon-based negative electrode, after about 5% of conductive polymer binder is added, the electron conductivity of the pole piece is highest, because after polymerization, the increase of the anthracene unit percentage in the molecule improves the conductivity of the polymer binder, provides a better electron transmission matrix for the silicon material in the electrode, and simultaneously suppresses the negative effect caused by the expansion of the silicon material. For the positive electrode, the electron conductivity of the pole piece is highest after about 4% of PSS is added, the PSS has strong adhesive force and adjustable mechanical property besides the pole piece conductivity, the volume change of the high-nickel positive electrode in the charging and discharging process can be effectively inhibited, the PSS content is insufficient in an electron transmission path, the content is too high, the dispersibility is poor, and the pole piece conductivity is reduced due to agglomeration of the binder. The results of the cycle life test are shown in table 2, and it can be seen that the assembled solid state battery has the best cycle life by adding the conductive polymer binder to both the positive and negative electrodes. The results show that the method provided by the invention can effectively improve the conductivity and the cycle life of the solid battery, and provides a path reference for the research of the high-performance solid battery.
Table 1. Positive and negative plate conductivity comparison table:
table 2. Comparative table of cycle life of solid batteries of different ratios:
it will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (7)
1. A method for preparing a solid state battery comprising a conductive polymer binder, comprising the steps of:
step 1, preparing a water-soluble anode conductive polymer binder and an anode: firstly, sodium carboxymethylcellulose CMC is dissolved in deionized water, and the mass fraction of CMC is 2-4%; dissolving sodium persulfate Na2S2O8 in a proper amount of deionized water, wherein the mass fraction of Na2S2O8 is 0.1-0.4%, mixing benzyl methacrylate, CMC solution, polyethylene glycol octyl phenyl ether Triton X-100 and deionized water according to the mass ratio of 10-20:25-35:2-3:70-85, magnetically stirring for 10-30 minutes at normal temperature to obtain a stable emulsion, heating the emulsion to 60-90 ℃ under argon or nitrogen atmosphere, adding sodium persulfate solution, wherein the mass ratio of the sodium persulfate solution is 1-3% of the total mixed solution, ultrasonically mixing for 20-40 minutes, continuously dropwise adding benzyl methacrylate and sodium persulfate solution while ultrasonically mixing, wherein the mass ratio of the added benzyl methacrylate and sodium persulfate solution is 12-35% and 10-25% of the total mixed solution respectively, ultrasonically dispersing the obtained mixed solution at 70-85 ℃ and 80-95 ℃ for 1-1.5 hours under argon atmosphere or nitrogen atmosphere, and cooling to obtain a water-soluble conductive polymer emulsion; silicon nano particles, graphite particles, water-soluble conductive polymer emulsion, carbon conductive agent and deionized water are mixed according to the mass ratio of 30-45:40-45:5-15:1-5:50-70 are added into a high-energy ultrasonic ball mill together, ball milling is carried out for 10-30 minutes at normal temperature, thus obtaining uniformly mixed negative electrode slurry, and the obtained slurry is coated on a negative electrode current collector by a scraper method, thus obtaining a negative electrode plate;
step 2, preparing a positive electrode containing a conductive polymer binder of the poly PSS: dissolving poly PSS in N-methyl pyrrolidone to form a glue solution, wherein the mass fraction of the PSS is 5-10%, adding the glue solution, a high-nickel ternary positive electrode material, lanthanum lithium zirconate LLZO or lanthanum lithium titanate LLTO or titanium aluminum lithium phosphate LATP, and a carbon conductive agent into a high-energy vibration ball mill together, ball milling for 10-30 minutes at normal temperature to obtain a uniformly mixed positive electrode slurry, and coating the positive electrode slurry on a positive electrode current collector to obtain a positive electrode plate;
step 3, assembling a solid battery: and (3) respectively pressing the positive and negative plates prepared in the step (1) and the step (2) on two sides of the solid electrolyte under 200-400 and standard atmospheric pressure, and assembling to obtain the button solid lithium battery.
2. The method for preparing a solid state battery containing a conductive polymer binder according to claim 1, wherein the silicon nanoparticles have a particle diameter of 200-800nm.
3. The method of manufacturing a solid state battery containing a conductive polymer binder according to claim 2, wherein the sodium persulfate is replaced with potassium persulfate.
4. The method for preparing a solid battery containing a conductive polymer binder according to claim 2, wherein the ball-material ratio in the step 1 is 1-1.5:1.5-3.0, and the ball-milling beads are zirconium beads.
5. The method for preparing a solid battery containing a conductive polymer binder according to claim 2, wherein the thickness of the negative electrode current collector is 10-50 μm, the material is one of copper foil, mesh copper foil, stainless steel or mesh stainless steel, and the coating thickness is 50-250 μm.
6. The method for preparing a solid battery containing a conductive polymer binder according to claim 1, wherein the thickness of the positive electrode current collector is 10-50 μm, the material is one of copper foil, mesh copper foil, stainless steel or mesh stainless steel, and the coating thickness is 50-250 μm.
7. The method of claim 1, wherein the solid electrolyte comprises an oxide solid electrolyte, a sulfide solid electrolyte, a polymer solid electrolyte, or any other electrolyte that can be used in a solid lithium battery.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108232318A (en) * | 2018-01-30 | 2018-06-29 | 陕西煤业化工技术研究院有限责任公司 | A kind of production method of all solid state power lithium-ion battery |
| CN109004229A (en) * | 2018-08-03 | 2018-12-14 | 中国地质大学（武汉） | A kind of anode material for lithium-ion batteries additive and its positive electrode and lithium ion secondary battery |
| CN111384436A (en) * | 2018-12-28 | 2020-07-07 | 中信国安盟固利动力科技有限公司 | All-solid-state lithium ion battery with negative electrode coated with solid electrolyte slurry and preparation method thereof |
| WO2020143259A1 (en) * | 2019-01-10 | 2020-07-16 | 北京工业大学 | Preparation and application of polycarbonate-based polymer electrolyte |
| CN113013414A (en) * | 2021-02-26 | 2021-06-22 | 蜂巢能源科技有限公司 | Cobalt-free positive electrode slurry, preparation method thereof, positive plate and lithium ion battery |
| CN113394376A (en) * | 2021-06-16 | 2021-09-14 | 哈尔滨工业大学 | High-voltage-resistant solid-state battery composite positive electrode and preparation method thereof |
-
2021
- 2021-12-09 CN CN202111501786.1A patent/CN114420929B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108232318A (en) * | 2018-01-30 | 2018-06-29 | 陕西煤业化工技术研究院有限责任公司 | A kind of production method of all solid state power lithium-ion battery |
| CN109004229A (en) * | 2018-08-03 | 2018-12-14 | 中国地质大学（武汉） | A kind of anode material for lithium-ion batteries additive and its positive electrode and lithium ion secondary battery |
| CN111384436A (en) * | 2018-12-28 | 2020-07-07 | 中信国安盟固利动力科技有限公司 | All-solid-state lithium ion battery with negative electrode coated with solid electrolyte slurry and preparation method thereof |
| WO2020143259A1 (en) * | 2019-01-10 | 2020-07-16 | 北京工业大学 | Preparation and application of polycarbonate-based polymer electrolyte |
| CN113013414A (en) * | 2021-02-26 | 2021-06-22 | 蜂巢能源科技有限公司 | Cobalt-free positive electrode slurry, preparation method thereof, positive plate and lithium ion battery |
| CN113394376A (en) * | 2021-06-16 | 2021-09-14 | 哈尔滨工业大学 | High-voltage-resistant solid-state battery composite positive electrode and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 锂离子电池水性粘结剂的制备与性能研究;吴春林;;四川化工(第04期);全文 * |
| 锂离子电池硅基负极用聚合物粘结剂的研究进展;武兆辉;杨娟玉;闫坤;于冰;方升;史碧梦;;稀有金属(第08期);全文 * |
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