CN115241418A - Low-temperature double-ion battery and preparation method thereof - Google Patents
Low-temperature double-ion battery and preparation method thereof Download PDFInfo
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- CN115241418A CN115241418A CN202210891475.9A CN202210891475A CN115241418A CN 115241418 A CN115241418 A CN 115241418A CN 202210891475 A CN202210891475 A CN 202210891475A CN 115241418 A CN115241418 A CN 115241418A
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- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000007773 negative electrode material Substances 0.000 claims abstract description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 239000011734 sodium Substances 0.000 claims abstract description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 10
- 239000011591 potassium Substances 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 229920000327 poly(triphenylamine) polymer Polymers 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 3
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- 239000000203 mixture Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 25
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 24
- 239000007774 positive electrode material Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 23
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- 239000006228 supernatant Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 238000000967 suction filtration Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000011888 foil Substances 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 12
- 239000011889 copper foil Substances 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 9
- 239000011267 electrode slurry Substances 0.000 claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 9
- 239000006258 conductive agent Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
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- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
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- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- -1 aluminum ions Chemical class 0.000 claims description 5
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- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000013543 active substance Substances 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 229910001414 potassium ion Inorganic materials 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 235000012431 wafers Nutrition 0.000 claims description 3
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
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- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
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- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims 6
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims 3
- 229910010941 LiFSI Inorganic materials 0.000 claims 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims 1
- 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 claims 1
- 230000008569 process Effects 0.000 abstract description 18
- 239000010405 anode material Substances 0.000 abstract description 6
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- 238000003860 storage Methods 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
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- 238000011068 loading method Methods 0.000 description 5
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- NAMDIHYPBYVYAP-UHFFFAOYSA-N 1-methoxy-2-(2-methoxyethoxy)ethane Chemical group COCCOCCOC.COCCOCCOC NAMDIHYPBYVYAP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021201 NaFSI Inorganic materials 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WGXOASMCETVLRE-UHFFFAOYSA-N [N-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F.[N-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F.[Na+].[Na+] Chemical compound [N-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F.[N-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F.[Na+].[Na+] WGXOASMCETVLRE-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZVUDNZZGFYBQRA-UHFFFAOYSA-N dipotassium bis(trifluoromethylsulfonyl)azanide Chemical compound [K+].[K+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F ZVUDNZZGFYBQRA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 239000007772 electrode material Substances 0.000 description 1
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
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- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- KVFIZLDWRFTUEM-UHFFFAOYSA-N potassium;bis(trifluoromethylsulfonyl)azanide Chemical compound [K+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F KVFIZLDWRFTUEM-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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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
- 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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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
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Abstract
The low-temperature double-ion battery comprises a polytriphenylamine positive electrode and Ti 3 C 2 T x The electrolyte is an ether-based electrolyte of metal salts. The preparation method comprises the following steps: preparing polytriphenylamine anode material and Ti 3 C 2 T x The preparation method comprises the following steps of preparing a negative electrode material, preparing an electrode plate and preparing a battery. The double-ion battery avoids the desolvation process in the electrode reaction process by utilizing the synergistic action between the anode and the cathode and the electrolyte. Furthermore, by changing the electrolyte, theThe double-ion battery can realize the storage of lithium, sodium and potassium systems, and has wide application range. The double-ion battery has simple structure and reasonable design, and has higher working voltage, energy density, power density and stable cycle performance at low temperature (-20 ℃ to-60 ℃).
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage devices, and particularly relates to a low-temperature double-ion battery and a preparation method thereof.
Background
In recent years, energy storage devices with strong environmental adaptability and excellent low-temperature performance become one of the core powers for promoting the development of the fields of exploration in polar regions, deep space and high latitude areas, military affairs, aviation and the like. However, the secondary batteries mainly including lithium ion batteries have problems of energy density, rapid power density decay, significant cycle life reduction, and failure of normal charging at low temperature. And because the storage capacity of lithium element in the earth crust is low, the production cost of the lithium ion battery will rise year by year along with the year expansion of the 3C portable electronic product and new energy automobile markets, and therefore, a novel energy storage technology needs to be developed urgently.
Different from the traditional 'rocking chair type battery' working principle, the anions and the cations in the double-ion battery can participate in the reaction between the anode and the cathode at the same time. Anions in the electrolyte during charging (e.g. PF 6) - 、FSI - Etc.) to the positive electrode, and a cation (e.g., li) + 、Na + 、K + Etc.) move to the negative electrode, and embedding reaction occurs at the two ends of the positive electrode and the negative electrode; during discharging, anions and cations are simultaneously extracted from the anode and the cathode and return to the electrolyte. In addition, cations in the electrolyte may undergo a solvation reaction with the solvent to form solvated ions. In the electrode reaction process, a desolvation process can occur when solvated ions reach an electrode interface, and the process has a higher reaction activation energy barrier at a low temperature and becomes a speed control step in the electrode reaction process; in the bi-ion battery, the free anions can be directly embedded into the anode material, thereby avoiding the electrode process, however, the cathode side is exposed to a desolvation process with high activation energy barrier as in the rocking chair type battery. Therefore, the mismatch of the kinetic mechanism between the positive electrode and the negative electrode is one of the key factors limiting the application of the bi-ion battery at low temperature.
Graphite is a main positive electrode material of the bi-ion battery, and although the graphite has the advantages of low cost, good conductivity and the like, the high working potential (5.0V) of the graphite causes instability of electrolyte and poor cycle performance. For the existing negative electrode, carbon materials such as graphite, hard carbon and the like have good electrochemical performance, but have poor multiplying power performance and low working potential (about 0.1V), and metal dendrite is easily formed on the surface at low temperature, so that potential safety hazards are caused; the alloying reaction of metal base materials such as antimony and tin with alkali metal ions can cause the materials to have larger volume expansion and pulverization, fast capacity attenuation and poor rate capability. Therefore, a novel double-ion battery system is constructed, the dynamic mechanisms of the positive electrode and the negative electrode are matched, and technical support can be provided for the preparation of the high-performance low-temperature double-ion battery.
Disclosure of Invention
The invention aims to solve the problems of fast capacity fading, poor rate capability and short cycle life of a double-ion battery at low temperature, and provides a low-temperature double-ion battery and a preparation method thereof.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a low-temperature double-ion battery comprises a positive electrode, a negative electrode, a binder, a diaphragm and electrolyte, wherein the positive electrode active substance of the double-ion battery is an anion-embedded organic positive electrode material poly triphenylamine PTPAn, and the negative electrode active substance is ion-solvent co-embedded Ti 3 C 2 T x A material; the electrolyte is an ether-based electrolyte. The double-ion battery avoids the desolventizing process on the positive electrode and the negative electrode in the electrode reaction process, and the working temperature range of the device is minus 20 ℃ to minus 60 ℃.
Further, the anode and the cathode are prepared by mixing corresponding anode and cathode materials, a conductive agent and a binder; the positive and negative electrode binders are all sodium carboxymethyl cellulose (CMC); the diaphragm is made of glass fiber; the current collector of the positive electrode is an aluminum foil, and the current collector of the negative electrode is a copper foil. The anode and cathode materials, the conductive agent and the binder are prepared by mixing in order to realize extremely high electron conductivity; the binder is sodium carboxymethyl cellulose for enhancing the binding capacity of the electrode material and the current collector; the diaphragm is made of glass fiber to avoid short circuit of positive and negative electrodes caused by dendrite generated at low temperature; the selection of the ether electrolyte is the key for realizing the co-embedding of the cathode solvent and is matched with the working potential of the anode material; the selection of the positive and negative current collectors is to change the electrolyte only later to realize the storage of lithium, sodium and potassium systems, and because the aluminum foil can be used as the positive and negative current collectors in the sodium-potassium battery at the same time, and alloying reaction can occur when the aluminum is used as the negative current collector of the lithium battery.
Further, one of lithium ions, sodium ions, potassium ions, calcium ions, magnesium ions, or aluminum ions is dissolved in the electrolyte. The positive electrode of PTPAn is used for storing anions in electrolyte, and Ti 3 C 2 T x The negative electrode can store solvated metal ions such as lithium, sodium, potassium, calcium, magnesium, aluminum and the like.
Further, the metal salt in the electrolyte is lithium bis (fluorosulfonyl) imide (LiFSI) or sodium hexafluorophosphate (NaPF) 6 ) Potassium hexafluorophosphate (KPF) 6 ) Lithium bis (trifluoromethanesulfonylimide) (LiTFSI), sodium bis (fluorosulfonylimide) (NaFSI), sodium bis (trifluoromethanesulfonimide) (NaTFSI), potassium bis (fluorosulfonylimide) (KFSI) or potassium bis (trifluoromethanesulfonimide) (KTFSI).
Further, the solvent in the electrolyte is diethylene glycol dimethyl ether (Diglyme) or ethylene glycol dimethyl ether (DME).
Further, the electrolyte is NaPF 6 Diethylene glycol dimethyl ether and NaPF 6 Ethylene glycol dimethyl ether of LiFSI, KPF 6 And (3) ethylene glycol dimethyl ether of LiTFSI, ethylene glycol dimethyl ether of KFSI or diethylene glycol dimethyl ether of KFSI.
The preparation method of the low-temperature double-ion battery comprises the following steps:
the method comprises the following steps: weighing triphenylamine (TPAn) powder, adding the triphenylamine (TPAn) powder into chloroform solution, stirring and dissolving, and adding Fe 3+ : TPAn =4: weighing anhydrous ferric trichloride powder according to the molar ratio of 1, adding the solution under the protection of nitrogen atmosphere to perform polymerization reaction on TPAn, adding methanol into the solution after the reaction is finished, precipitating PTPAn, performing suction filtration, and putting the product (light yellow powder) into a vacuum containerDrying in an air drying box to obtain a positive electrode material PTPAn;
step two: the molar ratio of the components is 6-15: 1 weighing lithium fluoride (LiF) and Ti 3 AlC 2 Precursor, mixing the weighed LiF and concentrated hydrochloric acid (HCl) to prepare 6-9 mol L -1 The mixed solution of (1) is stirred uniformly, and then Ti is slowly added 3 AlC 2 Precursor, stirring the mixed solution at 25-45 ℃ for 24-72 h, transferring the mixed solution into a centrifuge tube, adding deionized water, centrifuging for 5-10 min at 3500-5000 rpm, removing supernatant, repeatedly centrifuging and washing until the pH value of the supernatant is 6 and the supernatant is dark green to obtain clayey precipitate, dispersing the precipitate in deionized water, carrying out ultrasonic treatment for 0.5-1 h under inert atmosphere and ice bath, centrifuging the dispersion liquid at 3500-5000 rpm for 30min, collecting dark green suspension with good dispersibility, and freeze-drying to obtain the negative electrode material Ti 3 C 2 T x ；
Step three: weighing the obtained positive and negative electrode materials, respectively mixing the positive and negative electrode materials with a conductive agent Super P and a binding agent CMC according to a certain proportion, uniformly mixing the mixture in a mortar according to a certain proportion, transferring the mixture into a weighing bottle, adding deionized water, uniformly stirring the mixture at room temperature to obtain viscous electrode slurry, and then respectively coating the viscous electrode slurry on a batch of aluminum foils and copper foils (the loading capacity is about 2-4 mg cm) -2 ) Then, drying the anode and cathode plates in a vacuum drying oven, and stamping the dried anode and cathode plates into wafers with the diameter of 14mm to obtain button cell electrodes;
step four: the obtained PTPAn positive electrode and activated Ti were put in a glove box 3 C 2 T x And the negative electrode, the glass fiber diaphragm and the ether-based electrolyte are assembled into the button type bi-ion battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) The present invention provides a bi-ion battery system utilizing Ti on the negative electrode side 3 C 2 T x The material ion-solvent co-embedding mechanism effectively accelerates the dynamic characteristics of the low-temperature cathode, enables the anode and cathode reaction dynamic mechanisms to be matched, and effectively improves the rate performance of the dual-ion full battery at low temperature.
(2) The double-ion battery system selects ether-based electrolyte with strong solvation capacity and an organic positive electrode material. On one hand, the anode material is coupled with the energy level orbit of the electrolyte, so that the decomposition of the electrolyte is avoided; on the other hand, the electrolyte with strong solvation capacity is utilized, so that the whole electrode reaction avoids a desolvation process, and the polarization generated in the electrode process at low temperature is reduced, thereby inhibiting the generation of dendritic crystals, and therefore, the double-ion full battery has excellent cycle stability at low temperature.
(3) The method is simple, effective, economical and practical, can realize electrochemical energy storage of lithium, sodium, potassium and other systems by simply replacing the electrolyte components of the double-ion battery, and has obvious application effect of the device at low temperature.
Drawings
FIG. 1 is a FTIR chart of a polytriphenylamine positive electrode material prepared in example 1 of the present invention;
FIG. 2 is Ti prepared in example 1 of the present invention 3 C 2 T x An XRD pattern of the negative electrode material;
FIG. 3 is Ti prepared in example 1 of the present invention 3 C 2 T x SEM image of the negative electrode material;
FIG. 4 is a NaPF solution prepared in example 1 of the present invention 6 The charging and discharging curve diagram of the double-ion battery with the Diglyme as the electrolyte at-25 ℃ (0.05 Ag -1 )；
FIG. 5 is a NaPF solution prepared in example 1 of the present invention 6 The cycle performance curve diagram of the double-ion battery with the Diglyme as the electrolyte at-25 ℃ (0.2 Ag -1 And 1.0Ag -1 Magnification);
FIG. 6 is a solution of NaPF prepared in example 1 of the present invention 6 The multiplying power performance curve diagram of the double-ion battery taking the Diglyme as the electrolyte at-40 ℃;
FIG. 7 is a solution of NaPF prepared in example 1 of the present invention 6 The cycle performance curve diagram of the double-ion battery with the Diglyme as the electrolyte at-40 ℃ (0.5 Ag -1 Multiplying power);
FIG. 8 is a NaPF solution prepared in example 2 of the present invention 6 DME as an electrolyteA discharge curve chart of the ion battery at different current densities at-40 ℃;
FIG. 9 is a solution of NaPF prepared in example 2 of the present invention 6 The cyclic performance curve diagram of the dual-ion battery taking DME as electrolyte at-40 ℃ (0.5 Ag) -1 Magnification);
FIG. 10 is a charge-discharge curve diagram (0.05 Ag) of the polytriphenylamine positive electrode material prepared in example 3 of the present invention at-40 ℃ in a lithium ion half-cell using DME dissolved with LiFSI as electrolyte -1 )；
FIG. 11 shows the positive electrode material of poly triphenylamine prepared in example 4 of the present invention dissolved with KPF 6 Potassium ion half cell charge-discharge curve (0.05 Ag) with DME as electrolyte at-60 deg.C -1 )；
FIG. 12 is a graph of a sample prepared in accordance with example 4 of the present invention to dissolve KPF 6 The charging and discharging curve of the dual-ion battery taking DME as electrolyte at-60 ℃ (0.05 Ag) -1 )。
Detailed Description
The technical solutions of the present invention are further described below with reference to the drawings and the embodiments, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
The invention avoids the desolvation process in the electrode reaction process by reasonably designing a double-ion battery system and utilizing the synergistic action between the anode, the cathode and the electrolyte. In addition, the double-ion battery can realize the storage of lithium, sodium and potassium systems by changing the electrolyte, thereby effectively expanding the application range of the device. In addition, the dual-ion battery realized by the invention has excellent low-temperature performance, higher working voltage, energy density, power density and stable cycle performance at low temperature, effectively promotes the application of the dual-ion battery at low temperature, and further improves the practical value of the invention.
Example 1:
a preparation method of a sodium-based low-temperature double-ion battery comprises the following steps:
1. weighing 1.2266g of triphenylamine TPan, adding 20mL of chloroform into the triphenylamine TPan and stirring the mixture for 5min, weighing 3.22g of anhydrous ferric chloride, adding the anhydrous ferric chloride into the solution under the protection of nitrogen to perform a polymerization reaction on the TPan, and stirring the mixture for 12h under the protection of nitrogen. After the reaction is finished, adding anhydrous methanol into the solution to separate out the PTPAn, performing suction filtration, redissolving a suction filtration product by using chloroform, repeatedly removing impurities for 3-4 times, and drying the light yellow powder obtained by suction filtration in a vacuum drying oven at 60 ℃ for 12 hours to obtain a positive electrode material PTPAn;
2. according to the molar ratio of 12:1 weighing LiF and Ti 3 AlC 2 Precursor, mixing the weighed LiF with concentrated hydrochloric acid to prepare 9mol L -1 Transferring the mixed solution to a magnetic stirrer, stirring for 10min, and slowly adding Ti 3 AlC 2 Precursor, avoiding overheating in the process, and stirring the mixed solution at 45 ℃ for 72h. Then, transferring the mixed solution into a 50mL centrifuge tube, adding deionized water, centrifuging at 3500rpm for 10min, removing supernatant, repeatedly centrifuging and washing until the pH value of the supernatant is 6, wherein the supernatant is dark green to obtain clay-like precipitate, dispersing the precipitate in 250mL deionized water, performing ultrasonic treatment for 1h in an inert atmosphere and an ice bath, centrifuging the dispersion liquid at 3500rpm for 30min, collecting suspension with good dark green dispersibility, and freeze-drying to obtain the negative electrode material Ti 3 C 2 T x ；
3. Weighing the obtained positive and negative electrode materials, respectively mixing the positive and negative electrode materials with a conductive agent Super P and a binder CMC in a mortar in proportion, transferring the mixture to a weighing bottle, adding deionized water, and magnetically stirring the mixture for 12 hours at room temperature to obtain viscous electrode slurry. Then respectively coating the aluminum foil and the copper foil on a batch of smooth and flat aluminum foil and copper foil with consistent specifications (the loading capacity is about 2-4 mg cm) -2 ) Then the mixture is dried for 12 hours in a vacuum drying oven at 120 ℃. Stamping the dried positive and negative pole pieces into round pieces with the diameter of 14mm to obtain button cell electrodes;
4. the obtained PTPAn positive electrode and activated Ti were put in a glove box 3 C 2 T x Negative electrode, glass fiber diaphragm and 0.5mol L -1 NaPF 6 The diethylene glycol dimethyl ether electrolyte is assembled into the button type double-ion full battery.
The FTIR chart of the PTPAn cathode material prepared in the embodiment is shown in figure 1; this example prepares Ti 3 C 2 T x The XRD pattern of the cathode material is shown in figure 2; as shown in FIG. 3, ti 3 C 2 T x The nano-sheet structure with folds is beneficial to the subsequent wetting of electrolyte and the ion transmission of electrolyte phase; the low-temperature dual-ion battery prepared by the embodiment has the temperature of 0.05Ag at minus 25 DEG C -1 The charge-discharge curve at current density is shown in FIG. 4, and the corresponding energy density is 276Wh kg -1 (ii) a As shown in FIG. 5, the dual ion battery has a temperature of-25 deg.C and 0.2Ag -1 And 1.0Ag -1 The capacity retention rate is 97.5 percent and 97.5 percent respectively after 2500 cycles under the current density; the rate performance graph of the low-temperature dual-ion battery prepared in the embodiment at-40 ℃ is shown in fig. 6; as shown in FIG. 7, the dual-ion battery has a temperature of-40 ℃ and 0.5Ag -1 The capacity retention rate is 93.6 percent after the current density is cycled for 2000 times.
Example 2:
a preparation method of a sodium-based low-temperature double-ion battery comprises the following steps:
1. weighing 1.2266g of triphenylamine TPAn, adding 20mL of chloroform into the triphenylamine TPAn, stirring the mixture for 5min, weighing 3.22g of anhydrous ferric chloride, adding the anhydrous ferric chloride into the solution under the protection of nitrogen to perform polymerization reaction on the TPAn, and stirring the mixture for 12h under the protection of nitrogen. After the reaction is finished, adding anhydrous methanol into the solution to separate out the PTPAn, performing suction filtration, redissolving a suction filtration product by using chloroform, repeatedly removing impurities for 3-4 times in the way, and drying the light yellow powder obtained by suction filtration in a vacuum drying oven at 60 ℃ for 12 hours to obtain a positive electrode material PTPAn;
2. according to the molar ratio of 12:1 weighing LiF and Ti 3 AlC 2 Precursor, mixing weighed LiF and concentrated hydrochloric acid to prepare 9mol L -1 Transferring the mixed solution to a magnetic stirrer, stirring for 10min, and slowly adding Ti 3 AlC 2 Precursor, avoiding overheating in the process, and stirring the mixed solution at 45 ℃ for 72 hours. Then, the mixed solution is transferred to a 50mL centrifuge tube, deionized water is added, centrifugation is carried out for 10min at 3500rpm, supernatant is removed, and repeated centrifugation is carried out to wash the supernatantThe pH value is 6, the supernatant is dark green, a clayey precipitate is obtained, the precipitate is dispersed in 250mL of deionized water, ultrasonic treatment is carried out for 1h under inert atmosphere and ice bath, then the dispersion liquid is centrifuged for 30min at 3500rpm, suspension with good dark green dispersibility is collected, and a negative electrode material Ti is obtained after freeze drying 3 C 2 T x ；
3. Weighing the obtained positive and negative electrode materials, respectively uniformly mixing the positive and negative electrode materials with a conductive agent Super P and a binder CMC in a mortar according to a certain proportion, transferring the mixture into a weighing bottle, adding deionized water, and magnetically stirring the mixture for 12 hours at room temperature to obtain viscous electrode slurry. Then respectively coating the aluminum foil and the copper foil on a batch of smooth and flat aluminum foil and copper foil with consistent specifications (the loading capacity is about 2-4 mg cm) -2 ) Then the mixture is dried for 12 hours in a vacuum drying oven at 120 ℃. Punching the dried positive and negative pole pieces into wafers with the diameter of 14mm to obtain button cell electrodes;
4. in a glove box, the obtained PTPAn positive electrode and the activated Ti are placed 3 C 2 T x Negative electrode, glass fiber separator and 0.5mol L -1 NaPF 6 The ethylene glycol dimethyl ether is assembled into the button type double-ion full cell.
The discharge curve of the low-temperature dual-ion battery prepared in the embodiment under different current densities at-40 ℃ is shown in FIG. 8, and the maximum energy density is 281Wh kg -1 Maximum Power Density 2404Wh kg -1 (ii) a As shown in FIG. 9, the low-temperature dual-ion battery prepared in this example has a temperature of-40 ℃ and a silver concentration of 0.5Ag -1 The capacity retention rate is 92% after 4000 cycles under the current density.
Example 3:
a preparation method of a lithium-based low-temperature double-ion battery comprises the following steps:
1. weighing 1.2266g of triphenylamine TPAn, adding 20mL of chloroform into the triphenylamine TPAn, stirring the mixture for 5min, weighing 3.22g of anhydrous ferric chloride, adding the anhydrous ferric chloride into the solution under the protection of nitrogen to perform polymerization reaction on the TPAn, and stirring the mixture for 12h under the protection of nitrogen. After the reaction is finished, adding anhydrous methanol into the solution to separate out the PTPAn, performing suction filtration, redissolving a suction filtration product by using chloroform, repeatedly removing impurities for 3-4 times in the way, and drying the light yellow powder obtained by suction filtration in a vacuum drying oven at 60 ℃ for 12 hours to obtain a positive electrode material PTPAn;
2. and (2) according to a molar ratio of 12:1 weighing LiF and Ti 3 AlC 2 Precursor, mixing weighed LiF and concentrated hydrochloric acid to prepare 9mol L -1 Transferring the mixed solution to a magnetic stirrer, stirring for 10min, and slowly adding Ti 3 AlC 2 Precursor, avoiding overheating in the process, and stirring the mixed solution at 45 ℃ for 72h. Then, transferring the mixed solution into a 50mL centrifuge tube, adding deionized water, centrifuging at 3500rpm for 10min, removing the supernatant, repeatedly centrifuging and washing until the pH value of the supernatant is 6, wherein the supernatant is dark green to obtain clay-like precipitate, dispersing the precipitate in 250mL deionized water, performing ultrasonic treatment for 1h in an inert atmosphere and an ice bath, centrifuging the dispersion at 3500rpm for 30min, collecting suspension with good dark green dispersibility, and freeze-drying to obtain the negative electrode material Ti 3 C 2 T x ；
3. Weighing the obtained positive and negative electrode materials, respectively uniformly mixing the positive and negative electrode materials with a conductive agent Super P and a binder CMC in a mortar according to a certain proportion, transferring the mixture into a weighing bottle, adding deionized water, and magnetically stirring the mixture for 12 hours at room temperature to obtain viscous electrode slurry. Then respectively coating the aluminum foil and the copper foil on a batch of smooth and flat aluminum foil and copper foil with consistent specifications (the loading capacity is about 2-4 mg cm) -2 ) Then drying the mixture for 12 hours at 120 ℃ in a vacuum drying oven. Stamping the dried positive and negative pole pieces into round pieces with the diameter of 14mm to obtain button cell electrodes;
4. the obtained PTPAn positive electrode and activated Ti were put in a glove box 3 C 2 T x Negative electrode, glass fiber separator and 0.5mol L -1 And the ethylene glycol dimethyl ether of LiFSI is assembled into a button type double-ion full battery.
The half-cell assembled by the PTPAn anode and the lithium metal prepared in the embodiment is 0.05Ag at-40 DEG C -1 The activation is carried out under the current density, the first coulombic efficiency is 89.4 percent, and the specific discharge capacity can reach 76.7mAh g -1 As shown in fig. 10.
Example 4:
a preparation method of a potassium-based low-temperature double-ion battery comprises the following steps:
1. weighing 1.2266g of triphenylamine TPAn, adding 20mL of chloroform into the triphenylamine TPAn, stirring the mixture for 5min, weighing 3.22g of anhydrous ferric chloride, adding the anhydrous ferric chloride into the solution under the protection of nitrogen to perform polymerization reaction on the TPAn, and stirring the mixture for 12h under the protection of nitrogen. After the reaction is finished, adding anhydrous methanol into the solution to separate out the PTPAn, performing suction filtration, redissolving a suction filtration product by using chloroform, repeatedly removing impurities for 3-4 times in the way, and drying the light yellow powder obtained by suction filtration in a vacuum drying oven at 60 ℃ for 12 hours to obtain a positive electrode material PTPAn;
2. according to the molar ratio of 12:1 weighing LiF and Ti 3 AlC 2 Precursor, mixing the weighed LiF with concentrated hydrochloric acid to prepare 9mol L -1 Transferring the mixed solution to a magnetic stirrer, stirring for 10min, and slowly adding Ti 3 AlC 2 Precursor, avoiding overheating in the process, and stirring the mixed solution at 45 ℃ for 72h. Then, transferring the mixed solution into a 50mL centrifuge tube, adding deionized water, centrifuging at 3500rpm for 10min, removing supernatant, repeatedly centrifuging and washing until the pH value of the supernatant is 6, wherein the supernatant is dark green to obtain clay-like precipitate, dispersing the precipitate in 250mL deionized water, performing ultrasonic treatment for 1h in an inert atmosphere and an ice bath, centrifuging the dispersion liquid at 3500rpm for 30min, collecting suspension with good dark green dispersibility, and freeze-drying to obtain a negative electrode material Ti 3 C 2 T x ；
3. Weighing the obtained positive and negative electrode materials, respectively uniformly mixing the positive and negative electrode materials with a conductive agent Super P and a binder CMC in a mortar according to a certain proportion, transferring the mixture into a weighing bottle, adding deionized water, and magnetically stirring the mixture for 12 hours at room temperature to obtain viscous electrode slurry. Then respectively coating the aluminum foil and the copper foil on a batch of smooth and flat aluminum foil and copper foil with consistent specifications (the loading capacity is about 2-4 mg cm) -2 ) Then the mixture is dried for 12 hours in a vacuum drying oven at 120 ℃. Stamping the dried positive and negative pole pieces into round pieces with the diameter of 14mm to obtain button cell electrodes;
4. in a glove box, the obtained PTPAn positive electrode and the activated Ti are placed 3 C 2 T x Negative electrode, glass fiber separator and0.5mol L -1 KPF 6 the button type double-ion full battery is assembled by the ethylene glycol dimethyl ether.
The semi-cell assembled by the positive electrode of PTPAn and metal potassium prepared in the embodiment is 0.05Ag at-60 DEG C -1 The first coulombic efficiency is 72.6 percent and the specific discharge capacity can reach 65.2mAh g by activation under the current density -1 As shown in fig. 11; the low temperature dual ion battery prepared in this example was operated at-60 deg.C with 0.05A g -1 The charge/discharge curve at the current density is shown in FIG. 12, and the energy density is 245Wh kg -1 。
Claims (7)
1. A low-temperature double-ion battery comprises a positive electrode, a negative electrode, a binder, a diaphragm and electrolyte, and is characterized in that: the positive active substance of the double-ion battery is polytriphenylamine, and the negative active substance of the double-ion battery is Ti 3 C 2 T x A material; the electrolyte is an ether-based electrolyte.
2. A low temperature bi-ion battery as claimed in claim 1, wherein: the binder is sodium carboxymethyl cellulose; the diaphragm is made of glass fiber; the current collector of the positive electrode is an aluminum foil, and the current collector of the negative electrode is a copper foil.
3. A low temperature bi-ion battery as claimed in claim 1 or 2, wherein: one of lithium ions, sodium ions, potassium ions, calcium ions, magnesium ions or aluminum ions is dissolved in the electrolyte.
4. A low temperature bi-ion battery as claimed in claim 1, wherein: the metal salt in the electrolyte is one of bis-fluorosulfonyl imide lithium, sodium hexafluorophosphate, potassium hexafluorophosphate, bis-trifluoromethanesulfonyl imide lithium, bis-fluorosulfonyl imide sodium, bis-trifluoromethanesulfonyl imide sodium, bis-fluorosulfonyl imide potassium or bis-trifluoromethanesulfonyl imide potassium.
5. The low temperature bi-ion battery of claim 4, wherein: the solvent in the electrolyte is diethylene glycol dimethyl ether or ethylene glycol dimethyl ether.
6. A low temperature bi-ion battery as claimed in claim 1, wherein: the electrolyte is NaPF 6 Diethylene glycol dimethyl ether and NaPF 6 Ethylene glycol dimethyl ether of (1), ethylene glycol dimethyl ether of LiFSI, KPF 6 And (3) ethylene glycol dimethyl ether of LiTFSI, ethylene glycol dimethyl ether of KFSI or diethylene glycol dimethyl ether of KFSI.
7. A method for preparing a low-temperature bi-ion battery according to any one of claims 1 to 6, wherein: the method comprises the following steps:
the method comprises the following steps: weighing triphenylamine powder, adding the triphenylamine powder into chloroform solution, stirring and dissolving, and adding Fe 3+ : TPAn =4: weighing anhydrous ferric trichloride powder according to the molar ratio of 1, adding the solution under the protection of nitrogen atmosphere to enable TPAn to generate polymerization reaction, adding methanol into the solution after the reaction is finished, precipitating PTPAn, performing suction filtration, and drying a product to obtain a positive electrode material PTPAn;
step two: the molar ratio of the components is 6-15: 1 weighing lithium fluoride and Ti 3 AlC 2 Precursor, mixing the weighed LiF with concentrated hydrochloric acid and preparing into 6-9 mol L -1 The mixed solution of (2), the solution is stirred evenly, and then Ti is slowly added 3 AlC 2 Precursor, stirring the mixed solution at 25-45 ℃ for 24-72 h, transferring the mixed solution into a centrifuge tube, adding deionized water, centrifuging at 3500-5000 rpm for 5-10 min, removing supernatant, repeatedly centrifuging and washing until the pH value of the supernatant is 6 and the supernatant is dark green to obtain clay-like precipitate, dispersing the precipitate in deionized water, carrying out ultrasonic treatment for 0.5-1 h under inert atmosphere and ice bath, centrifuging the dispersion liquid at 3500-5000 rpm for 30min, collecting suspension with good dark green dispersibility, and freeze-drying to obtain the negative electrode material Ti 3 C 2 T x ；
Step three: weighing the obtained positive and negative electrode materials, respectively mixing the positive and negative electrode materials with a conductive agent Super P and a binding agent CMC according to a certain proportion, uniformly mixing the mixture in a mortar according to a certain proportion, transferring the mixture into a weighing bottle, adding deionized water, uniformly stirring the mixture at room temperature to obtain viscous electrode slurry, then respectively coating the viscous electrode slurry on a batch of aluminum foils and copper foils with consistent specifications, smoothness and smoothness, then placing the electrode slurry in a vacuum drying oven for drying, and stamping the dried positive and negative electrode plates into wafers with the diameter of 14mm to obtain button cell electrodes;
step four: the obtained PTPAn positive electrode and activated Ti were put in a glove box 3 C 2 T x And the negative electrode, the glass fiber diaphragm and the ether-based electrolyte are assembled into the button type bi-ion battery.
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