CN117038849A - High-magnification solid electrolyte silicon integrated electrode, preparation method and application - Google Patents
High-magnification solid electrolyte silicon integrated electrode, preparation method and application Download PDFInfo
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- CN117038849A CN117038849A CN202311302431.9A CN202311302431A CN117038849A CN 117038849 A CN117038849 A CN 117038849A CN 202311302431 A CN202311302431 A CN 202311302431A CN 117038849 A CN117038849 A CN 117038849A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 90
- 239000010703 silicon Substances 0.000 title claims abstract description 83
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 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 abstract description 67
- 239000003792 electrolyte Substances 0.000 claims abstract description 53
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims abstract description 46
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 23
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 23
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims abstract description 23
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 20
- 239000006258 conductive agent Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 239000011267 electrode slurry Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 4
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000012983 electrochemical energy storage Methods 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 13
- 238000013461 design Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 21
- 229910001416 lithium ion Inorganic materials 0.000 description 21
- 150000002500 ions Chemical class 0.000 description 15
- 238000011056 performance test Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 230000037427 ion transport Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- URZWHNFFWSYUMB-UHFFFAOYSA-B aluminum lithium silicon(4+) titanium(4+) tetraphosphate Chemical compound P(=O)([O-])([O-])[O-].[Si+4].[Ti+4].[Al+3].[Li+].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-] URZWHNFFWSYUMB-UHFFFAOYSA-B 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229920005570 flexible polymer Polymers 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- DYKZEUFKJOSFSH-UHFFFAOYSA-K P([O-])([O-])([O-])=O.[Al+3].[Li+] Chemical compound P([O-])([O-])([O-])=O.[Al+3].[Li+] DYKZEUFKJOSFSH-UHFFFAOYSA-K 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
Classifications
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a high-magnification solid electrolyte silicon integrated electrode, a preparation method and application thereof, wherein the solid electrolyte silicon integrated electrode comprises a negative electrode and a solid electrolyte; the raw materials of the negative electrode comprise silicon powder, titanium aluminum lithium phosphate, a conductive agent and a binder; the solid electrolyte comprises lithium aluminum titanium phosphate, polyvinylidene fluoride-hexafluoropropylene and lithium salt as raw materials. According to the invention, through component modification of the electrode and the electrolyte and composite structural design, a solid electrolyte silicon integrated electrode with a firm electrode/electrolyte interface is constructed on the negative electrode in situ, so that the problem of poor multiplying power performance of the silicon-based solid-state battery is solved, and the preparation of the silicon-based solid-state battery with high capacity, high multiplying power and high safety supporting quick charge is realized. The high-rate solid electrolyte silicon integrated electrode prepared by the invention has a first-cycle discharge specific capacity of 3295.6mAh/g and a first-cycle efficiency of 72.6% under the 1C (1C=1000 mAh/g) rate, and the prepared battery still has a discharge specific capacity of 1980mAh/g under the 10C high rate.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high-rate solid electrolyte silicon integrated electrode, a preparation method and application.
Background
In order to meet and match electronic products requiring fast charging and high energy consumption, it is important to develop lithium ion batteries with high power density and high energy density. The theoretical specific capacity of the silicon negative electrode of the lithium ion battery is up to 3600 mAh/g, which is 10 times that of a commercial graphite negative electrode, and the silicon negative electrode can be used as the negative electrode to obviously improve the energy density of the lithium ion battery. However, the conventional liquid electrolyte cannot inhibit serious fracture and pulverization of silicon due to a huge volume change (300%) in the intercalation/deintercalation process, and also causes continuous growth of a Solid Electrolyte Interface (SEI) film at an electrode/electrolyte interface, continuously consumes a limited electrolyte, and increases internal resistance of a battery. In addition, the electrolyte is easy to cause negative electrode lithium precipitation when used at high multiplying power, so that the performance attenuation of the lithium ion battery is accelerated, and internal short circuit of the battery can be caused when serious, and fire explosion occurs.
The use of solid electrolytes can effectively avoid the above-mentioned disadvantages of organic electrolytes, with significant performance and safety advantages. However, ceramic-based solid electrolytes typified by oxides and sulfides have high hardness and very poor interface contact with silicon electrodes, resulting in high ion transfer resistance at the interface. In addition, since the silicon electrode side has no electrolyte, the ion transport resistance inside the electrode is also large. This results in poor rate performance of the solid-state battery.
Therefore, the problem of poor multiplying power performance of the silicon-based solid-state battery is solved by modifying the electrode and the electrolyte and structurally designing the electrode, and the preparation of the silicon-based solid-state battery with high capacity, high multiplying power and high safety supporting quick charge is realized and is the focus of the research of the current silicon-based electrode.
Disclosure of Invention
Aiming at the problems, the invention provides a high-rate solid electrolyte silicon integrated electrode and a preparation method thereof, which are used for improving the problem of poor ion conduction in a silicon negative electrode by compounding silicon and solid electrolyte, and the problem of using the same lithium ion conductor and polymer electrolyte to compound into a composite electrolyte, and reducing interface contact resistance while improving migration dynamics of ions at an electrode/electrolyte interface by constructing an integrated structure of the composite electrode and the composite electrolyte, so that the improvement of the rate performance of a battery is finally realized.
The first aspect of the invention provides a high-rate solid electrolyte silicon integrated electrode, which comprises a negative electrode and a solid electrolyte; the raw materials of the negative electrode comprise silicon powder, lithium aluminum titanium phosphate, a conductive agent and a binder; the solid electrolyte comprises lithium aluminum titanium phosphate, polyvinylidene fluoride-hexafluoropropylene and lithium salt as raw materials.
Preferably, the mass ratio of the silicon powder to the lithium aluminum titanium phosphate to the conductive agent to the binder is 1:0.5-1: 0.06-0.22:0.06-0.22. For example, there may be mentioned 1:0.5:0.06:0.06, 1:0.6:0.06:0.06, 1:0.7:0.06:0.06, 1:0.8:0.06:0.06, 1:0.9:0.06, 1:1:0.06:0.06, 1:0.5:0.1:0.06, 1:0.5:0.15:0.06, 1:0.5:0.2:0.06, 1:0.5:0.22:0.06, 1:0.5:0.06, 1:0.5:0.1, 1:0.06:0.15, 1:0.5:0.06:0.02, 1:0.5:0.06:0.22, 1:0.7:0.15:0.15, but not limited to the values mentioned, the values mentioned above, but other values not mentioned within the ranges of the values are equally applicable. More preferably, the mass ratio of the silicon powder to the lithium aluminum titanium phosphate to the conductive agent to the binder is 1:0.6-0.8:0.1-0.2:0.1-0.2.
The ion transmission impedance of the pure silicon electrode is larger, and the volume change of the silicon electrode is large, so that larger internal stress can be generated, and the interface stability of the electrode is affected. According to the invention, silicon powder and titanium aluminum lithium phosphate are compounded, carbon black is used as a conductive agent, polyacrylic acid is used as a binder, the prepared negative electrode has excellent initial coulombic efficiency and cycle performance, the lithium ion transmission impedance is low, lithium ions can be rapidly transferred into the electrode through the titanium aluminum lithium phosphate solid electrolyte, and the silicon can store charges more rapidly and fully. Meanwhile, the inventor finds that the lithium aluminum titanium phosphate has excellent mechanical properties, can effectively inhibit the volume expansion of silicon, and can further improve the stability of the electrode. However, the lithium aluminum titanium phosphate content cannot be excessive, otherwise the electron conductivity of the electrode is deteriorated, and the battery performance is adversely affected.
Preferably, the average particle size of the lithium aluminum titanium phosphate is 10-100 nm. For example, the average particle size of lithium aluminum titanium phosphate may be: 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm, but are not limited to the recited values, and other non-recited values within the range of values are equally applicable. More preferably, the average particle size of the lithium aluminum titanium phosphate is 30-80nm.
Preferably, the silicon powder is flaky silicon powder, the particle diameter of the flaky silicon powder is 1-20 um, and the thickness of the flaky silicon powder is 20-200 nm. Preferably, the silicon powder in the invention has a sheet diameter of 5um and a sheet thickness of 100 nm.
Preferably, the conductive agent is carbon black.
More preferably, the average particle diameter of the carbon black is 200 to 500nm. More preferably, the carbon black has an average particle diameter of 300 to 400nm. For example, the average particle diameter of carbon black may be exemplified by: 50 nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm, but are not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the binder is one of polyacrylic acid and polyvinylidene fluoride.
In order to effectively improve the stability of the negative electrode and further reduce the ion transmission resistance of the electrode, the binder is preferably polyacrylic acid. More preferably, the polyacrylic acid has a weight average molecular weight of 200000-600000 and a viscosity of 200-3000 cP.
Preferably, the mass ratio of the lithium aluminum titanium phosphate to the polyvinylidene fluoride to the hexafluoropropylene to the lithium salt is 1 (0.6-1.2) to 0.6-1. For example, the mass ratio of lithium aluminum titanium phosphate, polyvinylidene fluoride-hexafluoropropylene, and lithium salt may be: the values recited in 1:0.6:0.6, 1:0.6:0.7, 1:0.6:0.8, 1:0.6:0.9, 1:0.6:1, 1:0.7:0.6, 1:0.7:0.7, 1:0.8, 1:0.7:0.9, 1:0.7:1, 1:0.8:0.6, 1:0.8:0.7, 1:0.8:0.8, 1:0.8:0.9, 1:0.9:0.6, 1:0.9:0.7, 1:0.9:0.9, 1:0.9:1, 1:1:0.6, 1:1:0.7, 1:1:0.8, 1:0.9, 1:1:1.9, 1:1:1.6, 1:1:1:1:1.9, 1:1:1.6, 1:1:1.1:1:1.9, 1:1:2.9, 1:2.9, 1:1:1:1.9, 1:1:1:2.9, 1:2.9, 1:1:2.9, 1:1:1:2.9, 1:2.9, 1:1:1:2.9, 1:2.8, 2.8, 2:2.8, etc. are not the indicated by the above. More preferably, the mass ratio of the lithium aluminum titanium phosphate, the polyvinylidene fluoride-hexafluoropropylene and the lithium salt is 1:0.8-1.
According to the invention, lithium aluminum titanium phosphate, polyvinylidene fluoride-hexafluoropropylene and lithium salt are used as electrolyte raw materials, and particularly when the mass ratio of the lithium aluminum titanium phosphate to the polyvinylidene fluoride-hexafluoropropylene to the lithium salt is 1 (0.6-1.2) (0.6-1), and the lithium salt is lithium bistrifluoromethylsulfonimide, the solid electrolyte can be stably molded without pressure and has excellent interface performance, high ionic conductivity, electrochemical stability and excellent mechanical performance, and can greatly inhibit the volume expansion of a silicon electrode. The inventor analyzes that the titanium aluminum lithium phosphate is taken as a main filler, so that a lithium ion layer transmission channel is effectively provided, the ion conductivity is improved, and the multiplying power performance of the solid electrolyte can be greatly improved by more titanium aluminum lithium phosphate components; the mechanical property of the solid electrolyte is improved, the rigidity of the solid electrolyte is higher, the expansion of the silicon volume can be restrained in the charging and discharging process, the problem of capacity attenuation in the circulating process caused by pulverization and falling off due to the expansion of the silicon volume is solved, the combination between the silicon chip inside the silicon electrode and the lithium aluminum titanium phosphate is more compact, the conduction of ions is facilitated, the effect of high multiplying power is further realized, and the multiplying power and the circulating performance are improved. Lithium bis (trifluoromethylsulfonyl) imide serves as a lithium salt that provides free shuttling ions and serves to transport ions inside the battery. The polyvinylidene fluoride-hexafluoropropylene is used as a supporting matrix of the electrolyte, so that the solid electrolyte can be stably molded without pressure, and the solid electrolyte has excellent interface performance due to good flexibility; meanwhile, polyvinylidene fluoride-hexafluoropropylene has good electrochemical stability, and the existence of a strong electron-withdrawing functional group (-C-F-) is beneficial to the dissolution of lithium salt, and the strong dielectric property can support carriers with high concentration. However, the inventors have also found that the polyvinylidene fluoride-hexafluoropropylene content cannot be too high, probably because it is liable to form internal crystals of the polymer, and that the increase in the crystalline region rather inhibits the conduction of lithium ions. The inventors have unexpectedly found that lithium ion conductivity can be further improved and stability can be enhanced when lithium bistrifluoromethylsulfonyl imide is used in combination, and that lithium bistrifluoromethylsulfonyl imide is used as an organic salt, so that crystallization of a polymer can be inhibited while ions are provided, and a stable lithium ion transmission channel is maintained in the solid electrolyte, thereby improving ion conductivity and stability.
Preferably, the weight average molecular weight of the polyvinylidene fluoride-hexafluoropropylene is 200000-600000, and the melt index at 230 ℃ is 1-10 g/10 min.
Preferably, the lithium salt is one of lithium bistrifluoromethylsulfonyl imide, lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate and lithium dioxalate borate.
More preferably, the lithium salt is lithium bistrifluoromethylsulfonylimide.
The second aspect of the invention provides a preparation method of the solid electrolyte silicon integrated electrode, which comprises the following specific steps:
step S1: ball milling silica powder and lithium titanium aluminum phosphate in a protective atmosphere to obtain a first mixture; mixing the first mixture, the conductive agent and the binder, dispersing in water, and stirring to obtain negative electrode slurry; coating the negative electrode slurry on a substrate, and drying to obtain the negative electrode;
step S2: dissolving lithium aluminum titanium phosphate, polyvinylidene fluoride-hexafluoropropylene and lithium salt in a solvent, and stirring and mixing to obtain precursor slurry of the solid electrolyte;
step S3: pouring the solid electrolyte precursor slurry into a template fixed with a negative electrode, standing at room temperature, and drying to obtain the solid electrolyte silicon integrated electrode.
According to the invention, the solid electrolyte silicon integrated electrode with a firm electrode/electrolyte interface is constructed on the negative electrode in situ by directly pouring the composite electrolyte slurry on the silicon/titanium aluminum lithium phosphate composite negative electrode and evaporating the solvent. The introduction of the flexible polymer can improve interface contact of the electrode/electrolyte, reduce ion transfer resistance at the interface, and the electrode/electrolyte integrated structure can enable the interface to be firmer, the firmer electrode/electrolyte interface is beneficial to accelerating rapid migration of lithium ions at the interface, silicon is not easy to separate from solid electrolyte, and the method has positive effect on maintaining low interface contact resistance; the electrode and the electrolyte both contain lithium titanium aluminum phosphate, so that the component continuity and the structural integrity of the integrated electrode after the composition are ensured.
In order to further improve the first-turn coulombic efficiency of the electrode, preferably, in step S1, the silicon powder is subjected to heat treatment, wherein the heat treatment temperature is 900-1200 ℃, and the heat treatment time is 1-4 hours.
Preferably, in the step S1, the ball milling speed is 300-400 r/min, and the ball milling time is 4-8 h.
Preferably, in the step S1, the stirring speed is 600-1000 r/min, and the stirring time is 2-4 h.
Preferably, in step S1, the substrate is a copper foil.
Preferably, in step S1, the specific steps of drying are as follows: (1) carrying out forced air drying at the temperature of 40-80 ℃ for 1-4 hours; (2) And then vacuum drying is carried out for 12-14 h at the temperature of 80-110 ℃ and the vacuum degree is-0.02-0.085 MPa.
Preferably, the solvent in the step S2 is one of N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, and N, N-dimethylacetamide. In the present invention, the solvent used is not particularly limited. More preferably, the solvent is N, N dimethylformamide.
Preferably, in the step S2, the mass-volume ratio of the lithium aluminum titanium phosphate to the solvent is 0.1-0.2:1 g/mL.
Preferably, in the step S2, the stirring speed is 500-800 r/min, and the stirring time is 12-24 h.
Preferably, in the step S3, the standing time at room temperature is 4-8 hours, the drying temperature is 40-80 ℃, and the drying time is 8-12 hours.
The third aspect of the invention provides the high-rate solid electrolyte silicon integrated electrode or the application of the high-rate solid electrolyte silicon integrated electrode prepared by the preparation method in electrochemical energy storage.
Advantageous effects
(1) According to the invention, a proper amount of solid electrolyte particles are added into the silicon negative electrode to solve the problem of poor ionic conduction in the silicon negative electrode, and meanwhile, the solid electrolyte particles with the same components are compounded with the flexible polymer electrolyte to prepare the composite solid electrolyte; the solid electrolyte silicon integrated electrode with continuous and stable structure is prepared by modifying the components of the electrode and the electrolyte and designing a composite structure; the ion transfer resistance in the electrode and at the electrode/electrolyte interface can be effectively reduced, the problem of poor multiplying power performance of the silicon-based solid-state battery is solved, and the preparation of the silicon-based solid-state battery with high capacity, high multiplying power and high safety supporting quick charge is realized.
(2) The high-rate electrolyte/silicon integrated electrode prepared by the invention has higher capacity and extremely high rate performance. The high-rate solid electrolyte silicon integrated electrode prepared by the invention has a first-cycle discharge specific capacity of 3295.6mAh/g and a first-cycle efficiency of 72.6% under the 1C (1C=1000 mAh/g) rate, and the prepared battery still has a discharge specific capacity of 1980mAh/g under the 10C high rate.
Drawings
FIG. 1 is a scanning electron microscope image of the negative electrode of the solid electrolyte silicon integrated electrode prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of the solid electrolyte prepared in example 1 of the present invention;
FIG. 3 is a graph showing the impedance of the solid electrolyte prepared in example 1 of the present invention at room temperature;
FIG. 4 is an Arrhenius diagram of a solid electrolyte prepared in example 1 of the present invention;
FIG. 5 is an LSV curve of the solid electrolyte prepared in example 1 of the present invention;
FIG. 6 is a graph showing the first charge and discharge of the negative electrode according to example 1 of the present invention;
FIG. 7 is a high rate performance test chart of the solid electrolyte silicon integrated electrode prepared in example 1 of the present invention;
FIG. 8 is a graph showing the first charge and discharge of the negative electrode prepared in examples 1 and 2 of the present invention;
FIG. 9 is a high rate performance test chart of the solid electrolyte silicon integrated electrode prepared in examples 1 and 2 of the present invention;
fig. 10 is an XRD pattern of the solid electrolyte prepared in examples 1, 3 of the present invention;
FIG. 11 is a graph showing the impedance of the solid electrolyte prepared in examples 1 and 3 of the present invention at room temperature;
FIG. 12 is an Arrhenius diagram of the solid state electrolyte prepared in examples 1, 3 of the present invention;
FIG. 13 is a LSV graph of the solid state electrolyte prepared in examples 1, 3 of the present invention;
FIG. 14 is a high rate performance test chart of the solid electrolyte silicon integrated electrode prepared in examples 1 and 3 of the present invention;
fig. 15 is an XRD pattern of the solid electrolyte prepared in example 1, comparative example 1 of the present invention;
FIG. 16 is a high rate performance test chart of the solid electrolyte silicon integrated electrode prepared in example 1, comparative example 1 of the present invention;
fig. 17 is an XRD pattern of the solid electrolyte prepared in example 1, comparative example 2 of the present invention;
fig. 18 is a graph showing the impedance of the solid electrolyte prepared in example 1 and comparative example 2 of the present invention at room temperature;
FIG. 19 is an Arrhenius diagram of the solid electrolyte prepared in example 1, comparative example 2 according to the present invention;
FIG. 20 is a LSV graph of the solid electrolyte prepared in example 1, comparative example 2 of the present invention;
FIG. 21 is a high rate performance test chart of the solid electrolyte silicon integrated electrode prepared in example 1, comparative example 2 of the present invention;
FIG. 22 is a graph showing the impedance of the solid electrolyte prepared in example 1 and comparative example 3 of the present invention at room temperature;
FIG. 23 is a graph showing the first charge and discharge curves of the negative electrode prepared in example 1 and comparative example 3 of the present invention;
FIG. 24 is a graph showing the first charge and discharge curves of the negative electrode prepared in example 1 and comparative example 4 of the present invention;
FIG. 25 is a schematic diagram of a mold used in preparing an electrode according to example 1 of the present invention.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. 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. The invention is further illustrated with reference to specific embodiments.
Examples
Example 1
The first aspect of the present embodiment provides a high-rate solid electrolyte silicon integrated electrode, including a negative electrode and a solid electrolyte; the cathode comprises silicon powder, lithium aluminum titanium phosphate, a conductive agent and a binder, wherein the mass ratio of the silicon powder to the lithium aluminum titanium phosphate to the conductive agent to the binder is 1:0.6:0.1:0.1.
The silicon powder is sheet silicon powder, the sheet diameter is 5um, the sheet thickness is 100nm, and the silicon powder is purchased from Korea, and the model is MA-EN-AN-18; the average particle size of the lithium aluminum titanium phosphate is 50 nm, and the lithium aluminum titanium phosphate is obtained from Kodaku; the conductive agent is carbon black with an average particle size of 400nm, purchased from Zhengzhou Jing Hongxin energy source Co., ltd; the binder was polyacrylic acid having a weight average molecular weight of 450000, a viscosity of 350-2500cP, available from sigma aldrich under the designation 181285.
The solid electrolyte comprises the raw materials of lithium aluminum titanium phosphate, polyvinylidene fluoride-hexafluoropropylene and lithium salt, wherein the mass ratio of the lithium aluminum titanium phosphate to the polyvinylidene fluoride-hexafluoropropylene to the lithium salt is 1:0.8:0.8.
The average particle size of the lithium aluminum titanium phosphate is 50 nm, and the lithium aluminum titanium phosphate is obtained from Kodaku; the weight average molecular weight of polyvinylidene fluoride-hexafluoropropylene is 400000, the melt index at 230 ℃ is 3.5-7.5 g/10 min, and the polyvinylidene fluoride-hexafluoropropylene is purchased from Shanghai Ala Biochemical technology Co., ltd, and the MDL number is MFCD00212573; the lithium salt was lithium bis (trifluoromethylsulfonyl) imide, available from Shanghai Ala Biochemical technologies Co.
The second aspect of the embodiment provides a method for preparing a high-rate solid electrolyte silicon integrated electrode, which specifically comprises the following steps:
step S1: carrying out heat treatment on the silicon powder in an argon atmosphere for 3h, wherein the heat treatment temperature is 1000 ℃; ball-milling the treated 240 mg silicon powder and 144 mg titanium aluminum lithium phosphate under argon atmosphere to obtain a first mixture, wherein the ball-milling speed is 400 r/min, and the ball-milling time is 6h; mixing the first mixture, the conductive agent and the binder, dispersing in 2 ml water, and stirring for 3h under the condition of 800 r/min to obtain negative electrode slurry; coating the negative electrode slurry on a copper foil, wherein the coating thickness is 30 mu m; air-blasting and drying at 60 ℃ for 3 hours, and then vacuum-drying at 95 ℃ for 13 hours, wherein the vacuum degree is-0.02 MPa, so as to obtain the negative electrode;
step S2: dissolving lithium aluminum titanium phosphate, polyvinylidene fluoride-hexafluoropropylene and lithium salt in N, N-dimethylformamide, wherein the mass-volume ratio of the lithium aluminum titanium phosphate to the solvent is 0.15:1 g/mL;700 Stirring for 18h under r/min condition to obtain precursor slurry of the solid electrolyte;
step S3: pouring the solid electrolyte precursor slurry into a template (a mould design diagram is shown in figure 25) fixed with a negative electrode, standing for 6h at room temperature, and drying for 10h at 60 ℃ to obtain the solid electrolyte silicon integrated electrode.
Example 2
The first aspect of the present embodiment provides a high-rate solid electrolyte silicon integrated electrode, and the specific implementation manner is the same as that of embodiment 1, and the difference between the specific implementation manner and embodiment 1 is that the mass ratio of silicon powder, titanium aluminum lithium phosphate, a conductive agent and a binder in the negative electrode is 1:0.8:0.1:0.1.
A second aspect of this embodiment provides a method for manufacturing a high-rate solid electrolyte silicon integrated electrode, and the specific embodiment is the same as that of embodiment 1.
Example 3
The first aspect of this embodiment provides a high-rate solid electrolyte silicon integrated electrode, and the specific implementation is the same as that of embodiment 1, and is different from embodiment 1 in that the mass ratio of lithium aluminum titanium phosphate, polyvinylidene fluoride-hexafluoropropylene and lithium salt in the solid electrolyte is 1:0.8:0.8.
A second aspect of this embodiment provides a method for manufacturing a high-rate solid electrolyte silicon integrated electrode, and the specific embodiment is the same as that of embodiment 1.
Comparative example 1
The first aspect of the present embodiment provides a high-rate solid electrolyte silicon integrated electrode, and the specific implementation manner is the same as that of embodiment 1, and the difference between the specific implementation manner and embodiment 1 is that the mass ratio of silicon powder, titanium aluminum lithium phosphate, a conductive agent and a binder in the negative electrode is 1:0.2:0.1:0.1.
A second aspect of this embodiment provides a method for manufacturing a high-rate solid electrolyte silicon integrated electrode, and the specific embodiment is the same as that of embodiment 1.
Comparative example 2
The first aspect of this embodiment provides a high-rate solid electrolyte silicon integrated electrode, and the specific implementation is the same as that of embodiment 1, and is different from embodiment 1 in that the mass ratio of lithium aluminum titanium phosphate, polyvinylidene fluoride-hexafluoropropylene and lithium salt in the solid electrolyte is 0.2:0.8:0.8.
A second aspect of this embodiment provides a method for manufacturing a high-rate solid electrolyte silicon integrated electrode, and the specific embodiment is the same as that of embodiment 1.
Comparative example 3
The first aspect of this example provides a high-rate solid electrolyte silicon integrated electrode, and the specific embodiment is the same as example 1, and differs from example 1 in that the average particle size of lithium aluminum titanium phosphate in the negative electrode is 300 nm.
A second aspect of this embodiment provides a method for manufacturing a high-rate solid electrolyte silicon integrated electrode, and the specific embodiment is the same as that of embodiment 1.
Comparative example 4
The first aspect of this embodiment provides a high-rate solid electrolyte silicon integrated electrode, and the specific embodiment is the same as that of embodiment 1, and is different from embodiment 1 in that the binder in the negative electrode is carboxymethyl cellulose.
A second aspect of this embodiment provides a method for manufacturing a high-rate solid electrolyte silicon integrated electrode, and the specific embodiment is the same as that of embodiment 1.
Performance testing
1. Impedance performance test
Assembled stainless Steel Sheet (SS)/organic-inorganic composite electrolyte (CPE)/stainless Steel Sheet (SS) blocking battery, body resistance of the battery was measured by AC impedance method, wherein the frequency of the test was 1Hz-10 5 Hz. The ionic conductivity of the polymer electrolyte is calculated in conjunction with the formula.
Where R is a resistance value (intercept on x-axis) of the electrolyte membrane obtained by EIS, L is a thickness of the electrolyte membrane, and S is an area of the electrolyte membrane.
2. Electrochemical stability window
A lithium sheet (Li)/organic-inorganic composite electrolyte (CPE)/stainless Steel Sheet (SS) battery was assembled, and a stable voltage of the battery was measured by testing a linear sweep voltammetry, wherein a test frequency was 0.05 mV/s, and a voltage sweep range was 0-6V.
3. Cathode first-turn charge and discharge test
And (3) testing the charge and discharge of the first circle of the cathode: assembled lithium aluminum silicon-titanium phosphate/liquid electrolyte/lithium sheet half cell at 0.1C (1c=1000 mAh g -1 ) The first cycle capacity performance of the negative electrode was tested in the next cycle.
4. Electrode/electrolyte integrated high rate performance test
Electrode/electrolyte integration high rate performance test: and assembling the silicon-titanium aluminum lithium phosphate@titanium aluminum lithium phosphate-polyvinylidene fluoride hexafluoropropylene composite integrated electrode/lithium sheet half cell. The performance of the integrated electrodes at high rates was tested at 5 cycles of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C rates, respectively.
The electrodes of examples 1-3 were subjected to the above performance test with the electrodes of comparative examples 1-2, the electrode of comparative example 3 was subjected to the impedance performance test and the anode first-turn charge-discharge test, and the electrode of comparative example 4 was subjected to the anode first-turn charge-discharge test, with the test results shown in table 1 below.
According to the invention, through the integrated design of introducing the electrolyte into the electrode and integrating the electrode and the electrolyte, the integrated electrode capable of rapidly transmitting lithium ions is prepared, so that the normal operation of the battery at high current density is realized, and the help is provided for the development of the current rapid charging technology. In example 1, a composite electrode was prepared using silicon and lithium aluminum titanium phosphate, and the lithium aluminum titanium phosphate as an electrolyte provided more lithium ion transport channels inside the composite electrode in addition to silicon as an active material, solving the problem of unsmooth lithium ion transport inside the solid-state battery. In addition, the optimal proportion of the lithium aluminum titanium phosphate to the polyvinylidene fluoride-hexafluoropropylene is obtained by optimizing electrolyte components, and the integrated electrode is prepared by directly pouring the electrolyte to the previous negative electrode, wherein the interface contact between the electrode and the electrolyte layer is very tight, meanwhile, the interface is provided with higher component consistency because of the existence of the lithium aluminum titanium phosphate as one of the components, the conduction of lithium ions at the interface is facilitated, and the integrated electrode prepared in the mode not only can enable the lithium ions to quickly migrate in the electrode, but also can improve the conduction of ions at the interface, and greatly improve the multiplying power performance of the electrode. The electrolyte layer in the integrated electrode was tested to have ion conductivity as high as 5.2X10 -4 S cm -1 Possessing the lowest reaction activation energy and simultaneously possessing the highest electrochemical stability window (4.8V) (0.20 eV); the electrode layer shows 4071 mAh g in the first charge and discharge -1 Excellent specific discharge capacity; the integrated material further shows an ultra-high discharge specific capacity of 1980 at 10 ℃.
In example 2, we increased the ratio of lithium aluminum titanium phosphate in the electrode material, and the electrolyte composition was unchanged. The result shows that after the ratio of the titanium aluminum lithium phosphate in the electrode is increased, the capacity of the electrode material is reduced, because the positive effect of the excessive titanium aluminum lithium phosphate on improving the lithium ion transfer rate and the lithiation degree in the silicon negative electrode is limited, the excessive titanium aluminum lithium phosphate increases the electrode quality, so that the specific capacity of the electrode is reduced; in example 3, we reduced the ratio of lithium aluminum titanium phosphate in the electrolyte, and the electrode composition was unchanged. The results show that after the ratio of the lithium aluminum titanium phosphate in the electrolyte is reduced, each electrochemical property of the electrolyte presents different degrees of degradation, which proves the importance of the lithium aluminum titanium phosphate in the system; in comparative example 1, we greatly reduced the ratio of lithium titanium aluminum phosphate in the electrode, and the electrolyte composition was unchanged. The results show that the electrode has reduced first-turn capacity and almost lost high rate performance, which is caused by the fact that a small amount of lithium aluminum titanium phosphate inside the electrode cannot provide a complete and sufficient lithium ion path; in comparative example 2, we greatly reduced the ratio of lithium titanium aluminum phosphate in the electrolyte, and the electrode composition was unchanged. The result shows that the electrochemical performance of the electrolyte is poor, and the performance of high multiplying power after integration is still not ideal, which is caused by unsmooth conduction of lithium ions by the electrolyte layer of the integrated electrode; in comparative example 3, we increased the particle size of the titanium aluminum lithium phosphate used, since the titanium aluminum lithium phosphate is in irregular block shape, the accumulation of titanium aluminum lithium phosphate in the electrolyte is not compact any more due to large particles, on the other hand, in the electrode, the contact of titanium aluminum lithium phosphate and the silicon wafer is also affected, which is manifested by the reduction of the ionic conductivity of the electrolyte and the reduction of the first-turn capacity of the negative electrode; in comparative example 4, we used carboxymethyl cellulose as a binder, and since carboxymethyl cellulose is spot-bonded, it is shown that the first turn capacity of the negative electrode is reduced.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The high-magnification solid electrolyte silicon integrated electrode is characterized by comprising a negative electrode and a solid electrolyte; the raw materials of the negative electrode comprise silicon powder, lithium aluminum titanium phosphate, a conductive agent and a binder; the solid electrolyte comprises lithium aluminum titanium phosphate, polyvinylidene fluoride-hexafluoropropylene and lithium salt as raw materials.
2. The high-rate solid electrolyte silicon integrated electrode according to claim 1, wherein the mass ratio of the silicon powder of the negative electrode raw material, the titanium aluminum lithium phosphate, the conductive agent and the binder is 1:0.5-1: 0.06-0.22:0.06-0.22.
3. The high rate solid state electrolyte silicon integrated electrode of claim 1 wherein the binder is one of polyacrylic acid, polyvinylidene fluoride.
4. The high-rate solid electrolyte silicon integrated electrode according to claim 1, wherein the mass ratio of the lithium aluminum titanium phosphate, the polyvinylidene fluoride-hexafluoropropylene and the lithium salt of the raw materials of the solid electrolyte is 1:0.6-1.2:0.6-1.
5. The high-rate solid electrolyte silicon integrated electrode according to claim 1, wherein the lithium salt is one of lithium bistrifluoromethylsulfonyl imide, lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, and lithium dioxalate borate.
6. The high rate solid state electrolyte silicon integrated electrode of claim 1 wherein the lithium aluminum titanium phosphate has an average particle size of 10-100 nm.
7. The method for preparing a high-rate solid electrolyte silicon integrated electrode according to any one of claims 1 to 6, characterized by comprising the following specific steps:
step S1: ball milling silica powder and lithium titanium aluminum phosphate in a protective atmosphere to obtain a first mixture; mixing the first mixture, the conductive agent and the binder, dispersing in water, and stirring to obtain negative electrode slurry; coating the negative electrode slurry on a substrate, and drying to obtain the negative electrode;
step S2: dissolving lithium aluminum titanium phosphate, polyvinylidene fluoride-hexafluoropropylene and lithium salt in a solvent, and stirring and mixing to obtain precursor slurry of the solid electrolyte;
step S3: pouring the solid electrolyte precursor slurry into a template fixed with a negative electrode, standing at room temperature, and drying to obtain the solid electrolyte silicon integrated electrode.
8. The method for preparing a high-rate solid electrolyte silicon integrated electrode according to claim 7, wherein in the step S1, the silicon powder is subjected to heat treatment at 900-1200 ℃ for 1-4 hours.
9. The method for preparing a high-rate solid electrolyte silicon integrated electrode according to claim 7, wherein in the step S2, the mass-volume ratio of the lithium aluminum titanium phosphate to the solvent is 0.1-0.2:1 g/mL.
10. The use of a high-rate solid-state electrolyte silicon integrated electrode in electrochemical energy storage, wherein the high-rate solid-state electrolyte silicon integrated electrode is the high-rate solid-state electrolyte silicon integrated electrode according to any one of claims 1 to 6 or the high-rate solid-state electrolyte silicon integrated electrode prepared by the preparation method according to claim 7.
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