CN114975994B - Low-temperature quick-chargeable lithium ion battery anode material and preparation method and application thereof - Google Patents
Low-temperature quick-chargeable lithium ion battery anode material and preparation method and application thereof Download PDFInfo
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- CN114975994B CN114975994B CN202210691457.6A CN202210691457A CN114975994B CN 114975994 B CN114975994 B CN 114975994B CN 202210691457 A CN202210691457 A CN 202210691457A CN 114975994 B CN114975994 B CN 114975994B
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- ion battery
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- anode material
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 41
- 239000010405 anode material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000007773 negative electrode material Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 17
- 229910052798 chalcogen Inorganic materials 0.000 claims abstract description 11
- 150000001787 chalcogens Chemical class 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000011669 selenium Substances 0.000 claims abstract description 6
- 239000011593 sulfur Substances 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007774 positive electrode material Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000006258 conductive agent Substances 0.000 claims description 12
- 239000013543 active substance Substances 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 11
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000008247 solid mixture Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 5
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 229910013067 LiBF 4 At Inorganic materials 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- 229910013553 LiNO Inorganic materials 0.000 claims description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- 229910052714 tellurium Inorganic materials 0.000 abstract description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 9
- 150000004770 chalcogenides Chemical class 0.000 description 8
- 238000011056 performance test Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000006257 cathode slurry Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a lithium ion battery anode material capable of being charged and discharged rapidly at a low temperature, and a preparation method and application thereof, and belongs to the technical field of electrochemical energy storage materials. The invention uses chalcogen elements including sulfur, selenium, tellurium and SxSe y 、S x Te y 、Se x Te y As a raw material, the chalcogen material is amorphized by a metal doping method, and a novel amorphous sulfur-based lithium ion battery anode material capable of being rapidly charged and discharged in a low-temperature environment is developed. The amorphous chalcogen anode material of the lithium ion battery can be rapidly charged and discharged within the temperature range of-60 ℃ to 60 ℃, and simultaneously has higher specific charge-discharge capacity and cycle stability. The novel negative electrode can be matched with a positive electrode material and is applied to a low-temperature lithium ion battery full battery. The chalcogen material disclosed by the invention is rich in reserves and environment-friendly; the negative electrode material provided by the invention has the advantages of simple preparation process and low cost, and is suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of energy storage materials, in particular to a low-temperature quick-chargeable lithium ion battery anode material, a preparation method and application thereof.
Background
In recent years, electrochemical energy storage technology has been widely used with the development of electric automobiles, power energy storage and portable electronic products. Among them, lithium ion batteries having high energy density, high power density and high cycle stability are currently the most mature energy storage means, and are widely used in various industries.
However, a decrease in ambient temperature typically results in a decay in ion transport kinetics in the cell, which can cause problems including dramatic decreases in energy density, power density, and cycle life. The cathode material of the lithium ion battery has a critical influence on the performance of the battery at low temperature, the resistance of the traditional graphite cathode SEI film is increased under the low temperature environment, the electrochemical polarization is obviously aggravated, and Li + The diffusion rate in graphite is reduced and metallic lithium is easily precipitated on the surface of the negative electrode, so that the conventional graphite negative electrode is not an ideal negative electrode material for low-temperature lithium ion batteries.
Compared with the traditional graphite cathode, the chalcogen material has higher theoretical capacity, for example, the theoretical capacity of the sulfur simple substance is up to 1675mAh g -1 Meanwhile, the amorphous disordered structure is favorable for promoting the transmission of ions, and the amorphous chalcogenide material is hopeful to be used as a potential lithium ion anode material capable of being rapidly charged and discharged at low temperature.
Therefore, how to provide a lithium ion battery anode material capable of being rapidly charged and discharged in a low-temperature environment, and having excellent energy density, excellent power density and excellent cycle stability, and a preparation method and application thereof are technical problems to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a lithium ion anode material capable of being charged and discharged rapidly at low temperature and a preparation method thereof. The negative electrode material can be reversibly charged and discharged in a temperature environment of-60 ℃ to 60 ℃, and has excellent rate capability and cycle stability.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the lithium ion battery anode material capable of being rapidly charged and discharged at low temperature comprises an active substance, wherein the active substance is obtained by doping 0.1-50% of metal in a chalcogen material.
Preferably, the chalcogenide material is selected from sulfur, selenium, tellurium, S x Se y 、S x Te y 、Se x Te y One of the following; the metal is any one of Cr, mn, fe, co, ni, cu, zn, mo, ru, rh, pd, ag, pt and Au, wherein x is in the range of 0 < x < 1; the y range is 0 < y < 1.
More preferably, the metal-doped amorphous chalcogenide material is Fe-doped elemental sulfur.
Preferably, the anode material further comprises a conductive agent and a binder, wherein the mass ratio of the active material to the conductive agent and the binder is (6-9.6): (0.2-2): (0.2-2).
More preferably, the mass ratio of the active substance to the conductive agent to the binder is 7:2:1.
preferably, the conductive agent is one or more of SuperP, acetylene black, ketjen black, conductive graphite, carbon nanotubes, graphene and carbon fibers.
More preferably, the conductive agent is SuperP.
Preferably, the binder is selected from one or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyacrylic acid (PAA), carboxymethyl cellulose/sodium carboxymethyl cellulose (CMC), styrene-butadiene rubber (GR-S), sodium Alginate (SA), LA132 or gelatin.
More preferably, the binder is LA132.
Another object of the present invention is to provide a method for preparing the lithium ion battery anode material capable of being rapidly charged and discharged at a low temperature, comprising the following steps:
s1, weighing all raw materials in the anode material for standby;
s2, mixing the chalcogen material with metal, and adding water for full grinding to obtain an active substance;
s3, adding a conductive agent into the active substance, and continuously and fully grinding to uniformly mix the conductive agent and the active substance to obtain a solid mixture I;
s4, adding a binder into the solid mixture I, and continuously and fully grinding to uniformly mix the solid mixture I and the solid mixture II;
s5, adding a solvent into the solid mixture II, continuously and fully grinding and uniformly mixing to obtain composite slurry;
s6, coating the composite slurry on a copper current collector, and carrying out vacuum drying to obtain the anode material.
Preferably, the grinding time in the steps S2-S5 is 30-60min, and the solvent in the step S5 is deionized water.
More preferably, the milling time in steps S2-S5 is 60 minutes.
The invention also aims to provide the application of the low-temperature rapidly chargeable lithium ion battery anode material in a lithium ion battery.
Preferably, the low-temperature fast-chargeable lithium ion battery anode material can also be used for sodium ion batteries and potassium ion batteries.
Preferably, the lithium ion battery further comprises an electrolyte and a positive electrode material, wherein the electrolyte comprises lithium salt, an organic solvent and an additive.
Preferably, the lithium salt is selected from LiTFSI, liFSI, liCF 3 SO 3 、LiPF 6 、LiClO 4 、LiNO 3 、LiBF 4 At least one of LiDFOB and LiBOB;
the organic solvent is at least one selected from dimethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, 1,3 dioxolane, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, fluoroethylene carbonate, propylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate and vinylene carbonate;
the additive is 2, 2-trifluoroethyl-1, 2-tetrafluoroethyl ether with the volume content of 1-10 percent 1, 3-hexafluoroisopropyl methyl ether 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether at least one of 1H, 5H-octafluoropentyl-1, 2-tetrafluoroethyl ether.
More preferably, the electrolyte comprises a solution of LITFSI salt and DME, and the additive is 2, 2-trifluoroethyl-1, 2-tetrafluoroethyl ether with a volume content of 1%.
Compared with the prior art, the invention has the following beneficial effects:
1. the chalcogen material disclosed by the invention is rich in reserves, environment-friendly and is a promising lithium ion battery active material.
2. The amorphous disordered structure of the metal doped amorphous chalcogenide material is favorable for promoting the transmission of lithium ions, so that the amorphous chalcogenide material is a potential lithium ion negative electrode material capable of being charged and discharged rapidly at low temperature.
3. The metal doped amorphous chalcogenide material negative electrode material can be reversibly and rapidly charged and discharged within the temperature range of-60 ℃ to 60 ℃, and the charge-discharge multiplying power can reach 5 ℃ in the environment of-40 ℃.
4. The metal doped amorphous chalcogenide material anode material has excellent energy density, excellent power density and excellent cycle stability at the low temperature of minus 40 ℃.
5. The preparation method disclosed by the invention is simple to operate, low in production cost, mature in technology, capable of being put into production without a large amount of funds and technical investment, and relatively easy to industrialize. The preparation method based on the amorphous chalcogenide material has a huge application prospect in the mass production process of the battery anode material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph of capacity of a negative electrode material of the present invention at different current densities at room temperature;
FIG. 2 shows charge and discharge curves of the negative electrode material of the present invention at different current densities at room temperature;
FIG. 3 shows charge and discharge curves of the negative electrode material of the present invention under different current densities in a low temperature environment of-40 ℃;
FIG. 4 is a graph showing the cycle performance of the negative electrode material of the present invention at 0.2C in a low temperature environment of-40 ℃.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A lithium ion negative electrode material capable of being charged and discharged rapidly at low temperature comprises the following steps:
a. 99mg of elemental sulfur and 1mg of iron powder were taken, added with a small amount of water, sufficiently ground for 60 minutes, followed by vacuum drying in a vacuum oven at 60℃for 6 hours to obtain solid 1.
b. 70mg of solid 1 were taken, 20mg of SuperP was added, grinding was continued for 60min, followed by 10mg of PAA.
c. And c, adding a small amount of deionized water as a solvent into the solid obtained in the step b, and fully stirring for 60 minutes to obtain uniform negative electrode slurry.
d. And c, uniformly coating the slurry obtained in the step c on a Cu current collector by using a scraper, and then placing the current collector into a vacuum drying oven at 60 ℃ for drying for 12 hours to obtain the anode 1.
Example 2
A lithium ion negative electrode material capable of being charged and discharged rapidly at low temperature comprises the following steps:
a. 95mg of elemental selenium and 5mg of zinc powder are taken, a small amount of water is added for full grinding for 60min, and then the mixture is dried in vacuum in a vacuum drying oven at 60 ℃ for 6h, so that solid 2 is obtained.
b. 70mg of solid 1 was taken, 20mg of conductive graphite was added, grinding was carried out for 60 minutes, followed by 10mg of PTFE, and grinding was continued for 60 minutes.
c. And c, adding a small amount of deionized water as a solvent into the solid obtained in the step b, and fully stirring for 60 minutes or uniformly stirring the cathode slurry.
d. And c, uniformly coating the slurry obtained in the step c on a Cu current collector by using a scraper, and then placing the current collector into a vacuum drying oven at 60 ℃ for drying for 12 hours to obtain the anode 2.
Example 3
A lithium ion negative electrode material capable of being charged and discharged rapidly at low temperature comprises the following steps:
a. 99mg of elemental sulfur and 1mg of nickel powder were taken, added with a small amount of water, sufficiently ground for 60min, followed by vacuum drying in a vacuum oven at 60℃for 6h to obtain solid 1.
b. 80mg of solid 1 was taken, 10mg of carbon nanotubes were added, grinding was performed for 60min, followed by 10mg of CMC, and grinding was continued for 60min.
c. And c, adding a small amount of deionized water as a solvent into the solid obtained in the step b, and fully stirring for 60 minutes or uniformly stirring the cathode slurry.
d. And c, uniformly coating the slurry obtained in the step c on a Cu current collector by using a scraper, and then placing the current collector into a vacuum drying oven at 60 ℃ for drying for 12 hours to obtain the negative electrode 3.
Example 4
Room temperature electrochemical performance test for negative electrode material
The cathode 1 and a lithium sheet are assembled into a half battery through a diaphragm and electrolyte, wherein the diaphragm adopts a Celgard2325 diaphragm of the lithium ion battery; the electrolyte is prepared by dissolving 1M LiTFSI and 1% 2, 2-trifluoroethyl-1, 2-tetrafluoroethyl ether in DME.
The batteries were subjected to rate performance testing at room temperature of 25 ℃ at current densities of 0.2C,1C,2C,5C,10C,15C, respectively, where 1c=1675 mA/g. A capacity map (fig. 1) of the anode material under the room temperature condition at different current densities and a charge-discharge curve graph (fig. 2) of the anode material under the room temperature condition at different current densities are obtained. As can be seen from the graph, the negative electrode material has a capacity of about 800mAh/g at 0.2C, has a specific discharge capacity of about 400mAh/g at 15C, and shows excellent rapid charge and discharge performance.
Example 5
Temperature-changing electrochemical performance test for negative electrode material
The cathode 1 and a lithium sheet are assembled into a half battery through a diaphragm and electrolyte, wherein the diaphragm adopts a Celgard2325 diaphragm of the lithium ion battery; the electrolyte is prepared by dissolving 1M LiTFSI and 3% 2, 2-trifluoroethyl-1, 2-tetrafluoroethyl ether in DME.
The battery was subjected to rate performance test at-40 ℃ with current densities of 0.1C,1C, and 5C, respectively, to obtain charge and discharge curves of the negative electrode material shown in fig. 3 under different current densities at-40 ℃ low temperature environments. As can be seen from the graph, when the current density is 5C, the negative electrode material can be reversibly charged and discharged in a low-temperature environment of-40 ℃, and the specific discharge capacity is up to about 350mAh/g, which indicates that the negative electrode material is a lithium ion negative electrode material capable of being rapidly charged and discharged at a low temperature.
Example 6
The cycle performance test is carried out on the cathode material in the low-temperature environment of minus 40 DEG C
The cathode 1 and a lithium sheet are assembled into a half battery through a diaphragm and electrolyte, wherein the diaphragm adopts a Celgard2325 diaphragm of the lithium ion battery; the electrolyte is prepared by dissolving 1M LiTFSI and 3% 2, 2-trifluoroethyl-1, 2-tetrafluoroethyl ether in DME.
The battery was subjected to cycle performance test at a current density of 0.2C under a low temperature environment of-40 ℃. The cycle performance of the negative electrode material at 0.2C under the low temperature condition of-40 ℃ is obtained (figure 4). As can be seen from the graph, when the current density is 0.2C, the capacity of the negative electrode material is not obviously attenuated after more than 50 cycles of charge and discharge cycles at the low temperature of-40 ℃, which indicates that the negative electrode material has excellent cycle stability in a low-temperature environment.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The low-temperature fast-chargeable lithium ion battery anode material is characterized by comprising an active substance, wherein the active substance is obtained by doping 0.1-50% of metal in a chalcogen material;
the chalcogen material is selected from sulfur or selenium; the metal is one or more of Fe, ni and Zn;
the negative electrode material further comprises a conductive agent and a binder, wherein the mass ratio of the active material, the conductive agent and the binder is (6-9.6): (0.2-2): (0.2-2).
2. The low-temperature quick-chargeable lithium ion battery anode material according to claim 1, wherein the conductive agent is one or more of Super P, acetylene black, ketjen black, conductive graphite, carbon nanotubes, graphene and carbon fibers.
3. The low-temperature quick-chargeable lithium ion battery anode material of claim 2, wherein the binder is selected from one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, sodium carboxymethyl cellulose, styrene-butadiene rubber, sodium alginate, LA132 or gelatin.
4. The method for preparing the low-temperature rapid-chargeable lithium ion battery anode material as claimed in claim 3, comprising the following steps:
s1, weighing all the raw materials for standby;
s2, mixing the chalcogen material with metal, and adding water for full grinding to obtain an active substance;
s3, adding a conductive agent into the active substance, and continuously and fully grinding to uniformly mix the conductive agent and the active substance to obtain a solid mixture I;
s4, adding a binder into the solid mixture I, and continuously and fully grinding to uniformly mix the solid mixture I and the solid mixture II;
s5, adding a solvent into the solid mixture II, continuously and fully grinding and uniformly mixing to obtain composite slurry;
s6, coating the composite slurry on a copper current collector, and carrying out vacuum drying to obtain the anode material.
5. The method for preparing a low-temperature fast-chargeable lithium ion battery anode material according to claim 4, wherein the grinding time in the step S2-S5 is 30-60min, and the solvent in the step S5 is one of N-methylpyrrolidone and deionized water.
6. Use of a low temperature fast rechargeable lithium ion battery negative electrode material according to any of claims 2-3 in a lithium ion battery.
7. The use of a low temperature fast rechargeable lithium ion battery negative electrode material according to claim 6 in a lithium ion battery, wherein the lithium ion battery further comprises a positive electrode material and an electrolyte, wherein the electrolyte comprises a lithium salt, an organic solvent and an additive.
8. The use of a low temperature fast rechargeable lithium ion battery negative electrode material according to claim 7 in a lithium ion battery, wherein the lithium salt is selected from LiTFSI, liFSI, liCF 3 SO 3 、LiPF 6 、LiClO 4 、LiNO 3 、LiBF 4 At least one of LiDFOB and LiBOB;
the organic solvent is at least one selected from ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, 1,3 dioxolane, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, fluoroethylene carbonate, propylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate and vinylene carbonate;
the additive is 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether with the volume content of 1-10 percent 2, 2-trifluoroethyl-1, 2-tetrafluoroethyl ether 1, 3-hexafluoroisopropyl methyl ether one or more of 1H, 5H-octafluoropentyl-1, 2-tetrafluoroethyl ether.
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