CN114613996A - High-capacity molybdenum polysulfide composite positive electrode material for all-solid-state battery and preparation method and application thereof - Google Patents
High-capacity molybdenum polysulfide composite positive electrode material for all-solid-state battery and preparation method and application thereof Download PDFInfo
- Publication number
- CN114613996A CN114613996A CN202210223722.8A CN202210223722A CN114613996A CN 114613996 A CN114613996 A CN 114613996A CN 202210223722 A CN202210223722 A CN 202210223722A CN 114613996 A CN114613996 A CN 114613996A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- electrode material
- formula
- solid electrolyte
- mos
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 45
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000011733 molybdenum Substances 0.000 title claims abstract description 44
- 229920001021 polysulfide Polymers 0.000 title claims abstract description 44
- 239000005077 polysulfide Substances 0.000 title claims abstract description 44
- 150000008117 polysulfides Polymers 0.000 title claims abstract description 44
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000002203 sulfidic glass Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000010406 cathode material Substances 0.000 claims abstract description 23
- 229910003185 MoSx Inorganic materials 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 29
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910052787 antimony Inorganic materials 0.000 claims description 15
- 229910052718 tin Inorganic materials 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 229910052740 iodine Inorganic materials 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000012429 reaction media Substances 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 8
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 229910011201 Li7P3S11 Inorganic materials 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
- 239000010405 anode material Substances 0.000 description 9
- 239000012300 argon atmosphere Substances 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910001216 Li2S Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- XIPFMBOWZXULIA-UHFFFAOYSA-N pivalamide Chemical compound CC(C)(C)C(N)=O XIPFMBOWZXULIA-UHFFFAOYSA-N 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N carbon disulfide Substances S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Images
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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/362—Composites
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a high-capacity molybdenum polysulfide composite positive electrode material for an all-solid-state battery, which is prepared from molybdenum polysulfide and sulfide solid electrolyte by a liquid phase method; the molecular formula of the molybdenum polysulfide is MoSxWherein 5 is<x is less than or equal to 8. The composite cathode material provided by the invention can enable the contact between the electrode and the electrolyte to be more compact, and effectively improve the cycling stability of the lithium-sulfur all-solid-state battery. The preparation method of the composite anode materialThe method is simple and is suitable for wide popularization and application.
Description
Technical Field
The invention belongs to the technical field of all-solid-state batteries, and particularly relates to a high-capacity molybdenum polysulfide composite cathode material for all-solid-state batteries, and a preparation method and application thereof.
Background
It is well known that the use of fossil fuels brings about a number of environmental pollution problems, especially the greenhouse effect, affecting the global climate. The use of clean energy is a sustainable development trend, the energy storage technology is continuously updated and perfected as an important link of the storage and peak shaving of the clean energy, and the battery becomes a focused focus as a widely used energy storage technology.
The lithium-sulfur battery is one of a plurality of battery systems, has high theoretical capacity and high specific energy, and the all-solid-state battery structure can solve the problem that the lithium-sulfur battery has severe side reactions in charging and discharging. However, all-solid batteries have poor interfacial contact between electrodes and electrolytes, thereby limiting ion transport and ultimately leading to rapid capacity fade.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a high-capacity molybdenum polysulfide composite positive electrode material for an all-solid battery, and a preparation method and an application thereof.
The invention provides a high-capacity molybdenum polysulfide composite positive electrode material for an all-solid-state battery, which is prepared from molybdenum polysulfide and sulfide solid electrolyte by a liquid phase method;
the molecular formula of the molybdenum polysulfide is MoSxWherein 5 is<x≤8。
Preferably, the molybdenum polysulfide comprises MoS5.6，MoS5.7And MoS6One or more of (a).
Preferably, the sulfide solid electrolyte comprises one or more of a sulfide solid electrolyte with a general formula I, a sulfide solid electrolyte with a general formula II, a modified stance of the sulfide solid electrolyte with the general formula I and a modified stance of the sulfide solid electrolyte with the general formula II;
xLiaH·yCcDd·zP2S5formula I;
in the formula I, 0< x <100, 0< y <100, 0< z <100,
a is 1 or 2, c is 1 or 2, d is 1, 2 or 5,
h is S, Cl, Br or I,
c is Li, Si, Ge, P, Sn or Sb,
d is Cl, Br, I, O, S or Se;
rNapEe·sMmNn·tJjQquV formula II;
in formula II, 0< r <100, 0< s <100, 0< t <100, 0. ltoreq. u <100,
p is 1 or 2, e is 0, 1, 2 or 5, m is 1 or 2, n is 0, 1, 2 or 5, j is 1 or 2, q is 0, 1, 2 or 5,
e is S, Cl, Br or I,
m is P, Sb, Se, Ge, Si or Sn,
n is P, Sb, Se, Ge, Si or Sn,
j is P, Sb, Se, Ge, Si or Sn,
q is P, Sb, Se, Ge, Si or Sn,
v is S or P, and at least one of E and V is S.
Preferably, the mass of the sulfide solid electrolyte accounts for 0.1-60% of the mass of the composite positive electrode material.
The invention also provides a preparation method of the molybdenum polysulfide composite cathode material, which comprises the following steps:
mixing molybdenum polysulfide, sulfide solid electrolyte and a reaction medium, and then carrying out heating reaction to obtain a reaction product;
and carrying out heat treatment on the reaction product to obtain the composite cathode material.
Preferably, the reaction medium is selected from one or more of dimethylformamide, acetonitrile, acetone, tetrahydrofuran, hexafluoroisopropanol, ethanol, isopropanol, n-butanol, toluene, chlorobenzene, ethyl acetate, butyl butyrate, n-heptane and cyclohexanone.
Preferably, the temperature of the heating reaction is 30-220 ℃.
Preferably, the temperature of the heat treatment is 100-300 ℃, and the time is 0.1-10 hours.
The invention also provides an all-solid-state battery which comprises the molybdenum polysulfide composite cathode material.
Compared with the prior art, the invention provides a high-capacity molybdenum polysulfide composite anode material for an all-solid-state battery, which is prepared from molybdenum polysulfide and sulfide solid electrolyte by a liquid phase method; the molecular formula of the molybdenum polysulfide is MoSxWherein, 5<x is less than or equal to 8. The composite cathode material provided by the invention can enable the contact between the electrode and the electrolyte to be more compact, and effectively improve the cycling stability of the lithium-sulfur all-solid-state battery. The preparation method of the composite cathode material is simple and is suitable for wide popularization and application.
Drawings
FIG. 1 is a MoS prepared according to the present invention6Scanning electron microscope photographs of the positive electrode material;
FIG. 2 is a MoS prepared according to the present invention6EDS element analysis results of the cathode material;
FIG. 3 is a MoS prepared according to the present invention6X-ray diffraction peak pictures of the positive electrode material;
FIG. 4 shows MoS prepared in example 16@30％Li7P3S11SEM image of the positive electrode material;
FIG. 5 is the MoS prepared in example 16@30％Li7P3S11EDS mapping element distribution diagram of the anode material;
FIG. 6 is the MoS prepared in example 16@30％Li7P3S11The charge-discharge curve of the anode material under 100 mA/g;
FIG. 7 is the MoS prepared in example 16@30％Li7P3S11The cycle performance of the anode material under 100 mA/g;
FIG. 8 is the MoS prepared in example 26@15％Li7P3S11The charge-discharge curve of the anode material under 100 mA/g;
FIG. 9 is the MoS prepared in example 26@15％Li7P3S11The cycle performance of the anode material under 100 mA/g;
FIG. 10 is a MoS prepared in comparative example 16The charge-discharge curve of the anode material under 200 mA/g;
FIG. 11 is a comparisonMoS prepared in example 16Cycling performance of the positive electrode material at 200 mA/g.
Detailed Description
The invention provides a high-capacity molybdenum polysulfide composite positive electrode material for an all-solid-state battery, which is prepared from molybdenum polysulfide and sulfide solid electrolyte by a liquid phase method;
the molecular formula of the molybdenum polysulfide is MoSxWherein 5 is<x≤8。
In the present invention, x is selected from 5.1, 5.2, 5.5, 5.6, 5.7, 5.8, 6, 6.5, 7, 7.5, 8, or any value between 5< x.ltoreq.8.
In some embodiments of the invention, the molybdenum polysulfide comprises MoS5.6，MoS5.7And MoS6One or more of (a).
In the invention, the preparation method of the molybdenum polysulfide comprises the following three methods:
method 1): refluxing ammonium polythiomolybdate to obtain molybdenum polysulfide;
method 2): carrying out heat treatment on ammonium polythiomolybdate to obtain molybdenum polysulfide;
method 3): and mixing the solution of ammonium polythiomolybdate with the solution of an oxidant for reaction to obtain molybdenum polysulfide.
In the above method, the ammonium polythiomolybdate is not limited to (NH) which is self-made or commercially available4)2Mo2S12，(NH4)2Mo2S13One or more of (a).
Wherein, the method 1) specifically comprises the following steps:
ammonium polythiomolybdate and acetone are refluxed for 0.001 to 12 hours to form a dark suspension. And (4) collecting the dark precipitate after washing, and drying to obtain the cathode material.
In the present invention, the time of the reflux is preferably 0.001, 0.01, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 10, 12, or an arbitrary value between 0.001 and 12 hours.
The washing reagent may be one or more of methanol, ethanol, deionized water, carbon disulfide, acetone, dimethylformamide, diethyl ether and isopropanol.
The drying mode can be freeze drying or vacuum drying, and the drying time is 6-72 h, preferably 6, 12, 18, 24, 36, 48, 60, 72 or any value between 6-72 h.
Wherein, the method 2) specifically comprises the following steps:
and carrying out heat treatment on ammonium polythiomolybdate to obtain molybdenum polysulfide.
The temperature of the heat treatment is 100-400 ℃, preferably 100, 150, 200, 250, 300, 350, 400, or any value between 100-400 ℃, and the time is 0.001-12 hours, preferably 0.001, 0.01, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 10, 12, or any value between 0.001-12 hours. The atmosphere condition is inert gas.
Wherein, the method 3) is specifically as follows:
dissolving ammonium polythiomolybdate in an organic solvent to obtain an ammonium polythiomolybdate solution. Wherein the organic solvent is selected from one or more of dimethylformamide, dimethylacetamide and dimethylpropionamide.
And dissolving an oxidant in an organic solvent to obtain an oxidant solution. Wherein the oxidant is selected from elementary iodine, potassium permanganate, potassium dichromate, hydrogen peroxide, chlorine or S-containing2O8 2-One or more of (a) an oxidizing agent. The organic solvent is selected from one or more of dimethylformamide, dimethylacetamide and dimethylpropionamide.
Then, an oxidant solution is poured into the ammonium polythiomolybdate solution for reaction to obtain a precipitate, and the precipitate is washed, filtered and dried to obtain the cathode material.
The washing reagent may be one or more of methanol, ethanol, deionized water, carbon disulfide, acetone, dimethylformamide, diethyl ether and isopropanol.
The drying mode can be freeze drying or vacuum drying, and the drying time is 6-72 h, preferably 6, 12, 18, 24, 36, 48, 60, 72 or any value between 6-72 h.
The sulfide solid electrolyte comprises one or more of a sulfide solid electrolyte with a general formula I, a sulfide solid electrolyte with a general formula II, a modified stance of the sulfide solid electrolyte with the general formula I and a modified stance of the sulfide solid electrolyte with the general formula II;
xLiaH·yCcDd·zP2S5formula I;
in the formula I, 0< x <100, 0< y <100, 0< z <100,
a is 1 or 2, c is 1 or 2, d is 1, 2 or 5,
h is S, Cl, Br or I,
c is Li, Si, Ge, P, Sn or Sb,
d is Cl, Br, I, O, S or Se;
rNapEe·sMmNn·tJjQquV formula II;
in formula II, 0< r <100, 0< s <100, 0< t <100, 0. ltoreq. u <100,
p is 1 or 2, e is 0, 1, 2 or 5, m is 1 or 2, n is 0, 1, 2 or 5, j is 1 or 2, q is 0, 1, 2 or 5,
e is S, Cl, Br or I,
m is P, Sb, Se, Ge, Si or Sn,
n is P, Sb, Se, Ge, Si or Sn,
j is P, Sb, Se, Ge, Si or Sn,
q is P, Sb, Se, Ge, Si or Sn,
v is S or P, and at least one of E and V is S.
In some embodiments of the invention, the sulfide solid electrolyte is selected from 70Li2S·27P2S5·3P2O5、70Li2S·29P2S5·1P2O5、66.7Li2S·33.3P2S3、70Li2S·29P2S5·1P2S3、70Li2S·29P2S5·1Li3PO4，70Li2S·30P2S5、75Li2S·25P2S5And 63Li2S·27P2S510 LiBr.
In the present invention, the mass of the sulfide solid electrolyte accounts for 0.1% to 60% of the mass of the composite positive electrode material, and preferably, is any value between 0.1%, 0.5%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, or 0.1% to 60%.
In the invention, the particle size of the molybdenum polysulfide composite anode material is 1-50 μm.
The invention also provides a preparation method of the molybdenum polysulfide composite cathode material, which comprises the following steps:
mixing molybdenum polysulfide, sulfide solid electrolyte and a reaction medium, and then carrying out heating reaction to obtain a reaction product;
and carrying out heat treatment on the reaction product to obtain the composite cathode material.
Specifically, the method comprises the steps of firstly putting molybdenum polysulfide and sulfide solid electrolyte into a reactor, and then adding a reaction medium into the reactor.
Wherein the reaction medium comprises, but is not limited to, one or more of dimethylformamide, acetonitrile, acetone, tetrahydrofuran, hexafluoroisopropanol, ethanol, isopropanol, n-butanol, toluene, chlorobenzene, ethyl acetate, butyl butyrate, n-heptane, and cyclohexanone.
Then, the molybdenum polysulfide, the sulfide solid electrolyte and the reaction medium are mixed, and heating reaction is carried out.
The mixing method of the present invention is not particularly limited, and may be a mixing method known to those skilled in the art. In the invention, the mixing mode can be shaking and stirring, and the mixing time is 1-36 hours.
The temperature of the heating reaction is 30-220 ℃, and preferably is 30, 50, 70, 100, 120, 150, 180, 200, 220, or any value between 30-220 ℃.
And after the reaction is finished, removing the reaction medium to obtain a reaction product. Carrying out heat treatment on the reaction product, wherein the temperature of the heat treatment is 100-300 ℃, and preferably is 100, 150, 200, 250, 300, or any value between 100-300 ℃; the time is 0.1 to 10 hours, preferably 0.1, 0.5, 1, 2, 5, 10, or any value between 0.1 to 10 hours.
The invention also provides an all-solid-state battery which comprises the molybdenum polysulfide composite cathode material.
The high-capacity molybdenum polysulfide composite positive electrode material provided by the invention has excellent interface contact stability and stable structure in the battery charging and discharging process. The all-solid-state battery assembled by the composite anode material has high specific capacity and stable circulation.
For further understanding of the present invention, the following examples are provided to illustrate the high capacity molybdenum polysulfide composite cathode material for all-solid-state battery and the preparation method and application thereof, and the scope of the present invention is not limited by the following examples.
[ preparation of molybdenum polysulfide ]
0.28g of (NH)4)2Mo2S12Dissolving in 20ml of dimethylformamide; a solution of 0.2g iodine in 30mL of dimethylformamide was added to the above solution. The formation of a precipitate was immediately observed. Precipitated MoS6With DMF, CS2And acetone filtered and then lyophilized under argon for 36 h. The MoS6Has a particle diameter of 50 μm
As shown in FIG. 1, the Scanning Electron Microscope (SEM) picture shows MoS6The morphology of the material. The picture is obtained after the surface of a sample is plated with gold and bombarded by an electron beam under the accelerating voltage of 4kV, the collected signal is a secondary electron signal, and the amplification factor is 5000 times.
As shown in fig. 2, fig. 2 is an EDS elemental analysis result of the MoS6 positive electrode material prepared in example 1
As shown in FIG. 3, the X-ray diffraction peak pattern (XRD) shows MoS6The scanning range of the crystal structure of (2theta) is 5 to 80 degrees.
Example 1
[ PREPARATION OF POSITIVE ELECTRODE ]
Preparation of MoS6@30％Li7P3S11Composite positive electrode material:
in an argon atmosphere glove box (O)2<0.1ppm，H2O<0.1ppm), 0.1g of MoS60.014g of Li2S and 0.028g of P2S5Poured into a reaction vessel and 20ml of acetonitrile was added to the reaction vessel. The vessel was then sealed and heated to 50 ℃ with stirring for 24 hours. And removing acetonitrile after stirring, drying the mixture in a vacuum oven at 80 ℃ for 8 hours, and then carrying out heat treatment at 240 ℃ for 1 hour to obtain the composite cathode material.
0.08g of MoS were also taken in an argon atmosphere6/Li7P3S11Composite with 0.1g of Li10GeP2S12And 0.02g of super conductive carbon black are put into a mortar and mixed together in a manual grinding mode, and the final mixture is the composite of the cathode material.
As shown in FIG. 4, the Scanning Electron Microscope (SEM) picture is MoS6@30％Li7P3S11And (3) compounding the positive electrode material. The picture is obtained by bombarding the surface of a sample with electron beams under 8kV accelerated voltage after gold plating on the surface of the sample, the collected signals are secondary electron signals, and the amplification factor is 5000 times. As can be seen from FIG. 4, MoS6/Li7P3S11Composite material and MoS6Presents different morphologies, wherein the particle size of the composite cathode material is 20 +/-5 mu m.
FIG. 5 shows the distribution of S, Mo and P elements under the EDS mapping test.
[ preparation of Battery ]
The cell referred to in this example is an all-solid-state cell for electrochemical testing. The electrolyte used by the all-solid-state battery is a double-layer solid-state electrolyte, and 100mg of Li is firstly added10GeP2S12Cold pressing at 100MPa for about 10 seconds, and then mixing 50mg of 70Li2S-29P2S5-1P2O5Likewise using a pressure of 100MPa in Li10GeP2S12Forming a complete two-layer solid electrolyte.
1mg of the positive electrode material compound prepared by the method is uniformly paved on Li10GeP2S12Surface, cold pressing with 150 MPa. The negative electrode material used was lithium foil pressed at 50MPa to 70Li2S-29P2S5-1P2O5A side surface. The current collectors of the positive electrode and the negative electrode adopt stainless steel sheets. The above procedures were all carried out in an argon atmosphere glove box at room temperature. Through the above assembly steps, a complete all-solid-state battery can be obtained.
As shown in FIG. 6, the data plot shows the charge and discharge curves for the all-solid-state battery prepared in example 1, ranging from 1.0 to 3.0(vs Li/Li)+) The first, second, and twentieth cycles were recorded using a current density of 100mA/g, showing initial ultra-high specific charge/discharge capacities of 938.6mAh/g and 1346.5mAh/g, corresponding to an initial coulombic efficiency of 69.7%.
As shown in fig. 7, the data graph shows the cycle performance of the all-solid battery prepared in example 1, and the charge/discharge cycle test was performed at a current density of 100 mAh/g. After the first circulation, the coulomb efficiency starts to be obviously improved, and the specific charge/discharge capacity of the second circulation is 931.9mAh/g and 988.9mAh/g, and the coulomb efficiency is improved to be more than 99% in the 6 th circulation. Even after 20 times of charge/discharge cycles, the specific charge/discharge capacity can still reach 898.7mAh/g and 901.8 mAh/g.
Example 2
[ PREPARATION OF POSITIVE ELECTRODE ]
Preparation of MoS6@15％Li7P3S11Composite positive electrode material:
in an argon atmosphere glove box (O)2<0.1ppm，H2O<0.1ppm), 0.1g of MoS60.006g of Li2S and 0.012g of P2S5Poured into a reaction vessel and 20ml of acetonitrile was added to the reaction vessel. The vessel was then sealed and heated to 50 ℃ with stirring for 24 hours. And removing acetonitrile after stirring, drying the mixture in a vacuum oven at 80 ℃ for 8 hours, and then carrying out heat treatment at 240 ℃ for 1 hour to obtain the composite cathode material.
Also in an argon atmosphereIn (1), 0.08g of MoS is taken6/Li7P3S11Composite with 0.1g of Li10GeP2S12And 0.02g of super conductive carbon black are put into a mortar and mixed together in a manual grinding mode, and the final mixture is the compound of the cathode material.
[ preparation of Battery ]
The cell referred to in this example is an all-solid-state cell for electrochemical testing. The electrolyte used in the all-solid-state battery is a single-layer solid electrolyte containing 150mg of Li6PS5The Cl was cold pressed at 100MPa for about 10 seconds to form a complete monolayer solid electrolyte that was smooth on both sides. 1mg of the positive electrode material composite is uniformly paved on one side surface of the electrolyte, and cold pressing is carried out by 150 MPa. The negative electrode material was pressed against the other surface of the electrolyte at 50MPa using lithium foil. The current collectors of the positive electrode and the negative electrode adopt stainless steel sheets. The above procedures were all carried out in a glove box at room temperature under argon atmosphere. Through the above assembly steps, a complete all-solid-state battery can be obtained.
As shown in FIG. 8, the data plot shows the charge and discharge curves for the all-solid-state battery prepared in example 2, ranging from 1.0 to 3.0(vs Li/Li)+) The first, second, and twentieth cycles were recorded using a current density of 100mA/g, showing initial ultra-high specific charge/discharge capacities of 932.8mAh/g and 1275.1mAh/g, corresponding to an initial coulombic efficiency of 73.2%.
As shown in fig. 9, the data graph shows the cycle performance of the all-solid battery prepared in example 2, which was subjected to the charge/discharge cycle test at a current density of 100 mAh/g. After the first cycle, the coulombic efficiency began to increase significantly, and the specific charge/discharge capacity of the second cycle was 909mAh/g and 1001.8 mAh/g. The coulomb efficiency increased to over 99% in the fifteenth cycle. Even after 20 times of charge/discharge cycles, the specific charge/discharge capacity can still reach 812.2mAh/g and 815.6 mAh/g.
Example 3
[ preparation of molybdenum polysulfide ]
0.2g of (NH)4)2Mo2S12In the argon gas ringUnder the environment, heat treatment is carried out for 1h at 220 ℃ to obtain MoS5.7Said MoS5.7The particle size was 3 μm.
[ PREPARATION OF POSITIVE ELECTRODE ]
Preparation of MoS5.7@20％70Li2S·27P2S5·3P2O5Composite positive electrode material:
in an argon atmosphere glove box (O)2<0.1ppm，H2O<0.1ppm), 0.1g of MoS6And 0.025g of 70Li2S·27P2S5·3P2O5Poured into a reaction vessel and 20ml of acetonitrile was added to the reaction vessel. The vessel was then sealed and heated to 50 ℃ with stirring for 24 hours. And removing acetonitrile after stirring, and drying in a vacuum oven for 8 hours at 80 ℃ to obtain the composite cathode material.
0.08g of MoS were also taken in an argon atmosphere6/70Li2S·27P2S5·3P2O5Composite with 0.1g of Li10GeP2S12And 0.02g of super conductive carbon black are put into a mortar and mixed together in a manual grinding mode, and the final mixture is the compound of the cathode material.
[ preparation of Battery ]
The all-solid-state battery mentioned in this example was prepared in the same manner as in example 1, except that the positive electrode material composite prepared in example 3 was used.
Comparative example 1
[ PREPARATION OF POSITIVE ELECTRODE ]
In an argon atmosphere glove box (O)2<0.1ppm，H2O<0.1ppm), 0.4g of MoS was taken6With 0.5g of Li10GeP2S12And 0.1g of super conductive carbon black are put into a mortar and mixed together in a manual grinding mode, and the final mixture is the compound of the cathode material.
[ preparation of Battery ]
The all-solid-state battery mentioned in this comparative example was prepared in the same manner as in example 1, except that the positive electrode material composite prepared in comparative example 1 was used.
As shown in FIG. 10, the data plot shows the charge and discharge curves of the all-solid battery prepared in comparative example 1, ranging from 1.0 to 3.0(vs Li/Li)+) The first, second, and twentieth cycles were recorded using a current density of 200mA/g, showing initial ultra-high specific charge/discharge capacities of 944.8mAh/g and 1394.5mAh/g, corresponding to an initial coulombic efficiency of 67.8%.
As shown in fig. 11, the data graph shows the cycle performance of the all-solid battery prepared in comparative example 1, which was subjected to the charge/discharge cycle test at a current density of 200 mAh/g. After the first cycle, the coulombic efficiency began to increase slowly, and the specific charge/discharge capacity of the second cycle was 875.8mAh/g and 973.9 mAh/g. The coulomb efficiency increased to over 99% in the twentieth cycle, and the specific charge/discharge capacity reached 606.2mAh/g and 610.9 mAh/g.
As can be seen from the example data disclosed above, using MoSx(5<x is less than or equal to 8) and a sulfide solid electrolyte liquid phase method, and the prepared all-solid-state battery has more excellent cycle life and ultrahigh specific charge/discharge capacity at normal temperature.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (9)
1. A high-capacity molybdenum polysulfide composite positive electrode material for an all-solid-state battery is characterized in that the high-capacity molybdenum polysulfide composite positive electrode material is prepared from molybdenum polysulfide and sulfide solid electrolyte by a liquid phase method;
the molecular formula of the molybdenum polysulfide is MoSxWherein 5 is<x≤8。
2. The composite positive electrode material of claim 1, wherein the molybdenum polysulfide comprises MoS5.6，MoS5.7And MoS6One or more of (a).
3. The composite positive electrode material according to claim 1, wherein the sulfide solid electrolyte comprises one or more of a sulfide solid electrolyte having a general formula of formula I, a sulfide solid electrolyte having a general formula of formula II, a modification of a sulfide solid electrolyte having a general formula of formula I, and a modification of a sulfide solid electrolyte having a general formula of formula II;
xLiaH·yCcDd·zP2S5formula I;
in the formula I, 0< x <100, 0< y <100, 0< z <100,
a is 1 or 2, c is 1 or 2, d is 1, 2 or 5,
h is S, Cl, Br or I,
c is Li, Si, Ge, P, Sn or Sb,
d is Cl, Br, I, O, S or Se;
rNapEe·sMmNn·tJjQquV formula II;
in formula II, 0< r <100, 0< s <100, 0< t <100, 0. ltoreq. u <100,
p is 1 or 2, e is 0, 1, 2 or 5, m is 1 or 2, n is 0, 1, 2 or 5, j is 1 or 2, q is 0, 1, 2 or 5,
e is S, Cl, Br or I,
m is P, Sb, Se, Ge, Si or Sn,
n is P, Sb, Se, Ge, Si or Sn,
j is P, Sb, Se, Ge, Si or Sn,
q is P, Sb, Se, Ge, Si or Sn,
v is S or P, and at least one of E and V is S.
4. The composite positive electrode material according to claim 1, wherein the sulfide solid electrolyte is present in an amount of 0.1 to 60% by mass based on the mass of the composite positive electrode material.
5. A method for preparing the molybdenum polysulfide composite positive electrode material of any one of claims 1 to 4, comprising the steps of:
mixing molybdenum polysulfide, sulfide solid electrolyte and a reaction medium, and then carrying out heating reaction to obtain a reaction product;
and carrying out heat treatment on the reaction product to obtain the composite cathode material.
6. The method according to claim 5, wherein the reaction medium is selected from one or more of dimethylformamide, acetonitrile, acetone, tetrahydrofuran, hexafluoroisopropanol, ethanol, isopropanol, n-butanol, toluene, chlorobenzene, ethyl acetate, butyl butyrate, n-heptane and cyclohexanone.
7. The method according to claim 5, wherein the temperature of the heating reaction is 30 to 220 ℃.
8. The method according to claim 5, wherein the heat treatment is carried out at a temperature of 100 to 300 ℃ for 0.1 to 10 hours.
9. An all-solid-state battery comprising the molybdenum polysulfide composite positive electrode material of any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210223722.8A CN114613996B (en) | 2022-03-07 | 2022-03-07 | High-capacity molybdenum polysulfide composite positive electrode material for all-solid-state battery, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210223722.8A CN114613996B (en) | 2022-03-07 | 2022-03-07 | High-capacity molybdenum polysulfide composite positive electrode material for all-solid-state battery, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114613996A true CN114613996A (en) | 2022-06-10 |
| CN114613996B CN114613996B (en) | 2024-06-21 |
Family
ID=81861360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210223722.8A Active CN114613996B (en) | 2022-03-07 | 2022-03-07 | High-capacity molybdenum polysulfide composite positive electrode material for all-solid-state battery, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114613996B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108923031A (en) * | 2018-07-11 | 2018-11-30 | 中国科学院宁波材料技术与工程研究所 | A kind of transient metal sulfide combination electrode material and preparation method thereof and solid lithium battery |
| CN111082128A (en) * | 2019-12-23 | 2020-04-28 | 中国科学院青岛生物能源与过程研究所 | High-power all-solid-state battery and preparation thereof |
| CN114006027A (en) * | 2020-07-27 | 2022-02-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | Molybdenum disulfide-based composite solid electrolyte, and preparation method and application thereof |
-
2022
- 2022-03-07 CN CN202210223722.8A patent/CN114613996B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108923031A (en) * | 2018-07-11 | 2018-11-30 | 中国科学院宁波材料技术与工程研究所 | A kind of transient metal sulfide combination electrode material and preparation method thereof and solid lithium battery |
| CN111082128A (en) * | 2019-12-23 | 2020-04-28 | 中国科学院青岛生物能源与过程研究所 | High-power all-solid-state battery and preparation thereof |
| CN114006027A (en) * | 2020-07-27 | 2022-02-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | Molybdenum disulfide-based composite solid electrolyte, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| GAKU SHIROTA ET AL.: "Molybdenum polysulfide electrode with high capacity for all-solid-state sodium battery", 《SOLID STATE IONICS》, vol. 376, no. 115848, pages 1 - 7 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114613996B (en) | 2024-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109004229B (en) | Lithium ion battery positive electrode material additive, positive electrode material thereof and lithium ion secondary battery | |
| CN101521276A (en) | Method for producing lithium ion battery positive material coated with carbon | |
| CN110739427A (en) | Battery diaphragm material and preparation method and application thereof | |
| JPH08148185A (en) | Nonaqueous electrolyte secondary battery and negative electrode therefor | |
| CN107887590B (en) | Sulfur-carrying composite cathode material and preparation method and application thereof | |
| CN114204002A (en) | Composite coating method of high-compaction high-nickel layered cathode material for solid-state battery | |
| CN114552125A (en) | Nondestructive lithium supplement composite diaphragm and preparation method and application thereof | |
| CN113539694A (en) | Method for reducing oxidation potential of cathode pre-metallization, application of method and electrochemical energy storage device | |
| US20040146781A1 (en) | Electrode for secondary battery having intrinsic polymer electrolyte, method of producing the same, and secondary battery | |
| CN110024190B (en) | Electrode active material for nonaqueous secondary battery and nonaqueous secondary battery using same | |
| CN117374373A (en) | All-solid-state soft-package battery | |
| CN103534850A (en) | Electrodes for lithium batteries | |
| CN111416090A (en) | Perovskite oxide modified diaphragm material for lithium-sulfur battery and lithium-sulfur battery | |
| CN110661051B (en) | Solid-state battery material recovery processing method | |
| KR101748914B1 (en) | Lithium electrode, method for the same and lithium battery compring the same | |
| WO2022237106A1 (en) | Cobalt-free positive electrode material slurry, preparation method therefor and application technical field thereof | |
| CN114613996B (en) | High-capacity molybdenum polysulfide composite positive electrode material for all-solid-state battery, and preparation method and application thereof | |
| CN113594443B (en) | Phosphorus-metal poly phthalocyanine/carbon composite material and preparation method and application thereof | |
| CN115579504A (en) | Lithium-sulfur battery based on lithium supplement technology and without lithium metal negative electrode and application thereof | |
| JP3218285B2 (en) | Organic electrolyte battery | |
| CN110707383B (en) | Preparation method and use method of amorphous vanadium oxide/carbon fiber material for lithium-sulfur battery | |
| CN109616619B (en) | Method for producing lithium-sulfur battery electrodes with large active surface areas | |
| CN114597401B (en) | High-capacity molybdenum polysulfide composite positive electrode material, preparation method and application thereof in all-solid-state battery | |
| EP3546428B1 (en) | Method for manufacturing negative active material, and negative active material and lithium secondary battery using same | |
| CN115939375A (en) | High-capacity molybdenum polysulfide positive electrode material, preparation method and application thereof in all-solid-state battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |