CN112820935A - Novel battery based on sulfide solid electrolyte - Google Patents
Novel battery based on sulfide solid electrolyte Download PDFInfo
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- CN112820935A CN112820935A CN202011629806.9A CN202011629806A CN112820935A CN 112820935 A CN112820935 A CN 112820935A CN 202011629806 A CN202011629806 A CN 202011629806A CN 112820935 A CN112820935 A CN 112820935A
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- 239000002203 sulfidic glass Substances 0.000 title claims abstract description 37
- 239000007787 solid Substances 0.000 claims abstract description 183
- 239000011241 protective layer Substances 0.000 claims abstract description 85
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 65
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 49
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 48
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims description 72
- 239000003792 electrolyte Substances 0.000 claims description 65
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 47
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 33
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 27
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 25
- 238000003860 storage Methods 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 229910003002 lithium salt Inorganic materials 0.000 claims description 19
- 159000000002 lithium salts Chemical class 0.000 claims description 19
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 18
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- 235000010290 biphenyl Nutrition 0.000 claims description 15
- 239000004305 biphenyl Substances 0.000 claims description 15
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 12
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011244 liquid electrolyte Substances 0.000 claims description 12
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 12
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 11
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 10
- 150000004056 anthraquinones Chemical class 0.000 claims description 10
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
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- 239000002482 conductive additive Substances 0.000 claims description 9
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- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 6
- PZHIWRCQKBBTOW-UHFFFAOYSA-N 1-ethoxybutane Chemical compound CCCCOCC PZHIWRCQKBBTOW-UHFFFAOYSA-N 0.000 claims description 6
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 claims description 6
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 claims description 6
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 6
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 claims description 6
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- 229910013075 LiBF Inorganic materials 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002134 carbon nanofiber Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 6
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 6
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 6
- 229910001496 lithium tetrafluoroborate Inorganic materials 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
- 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 description 6
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
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- 238000002156 mixing Methods 0.000 claims description 6
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- 150000008116 organic polysulfides Chemical class 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 claims description 3
- 229910007860 Li3.25Ge0.25P0.75S4 Inorganic materials 0.000 claims description 3
- 229910013936 Li3.25P0.95S4 Inorganic materials 0.000 claims description 3
- 229910011899 Li4SnS4 Inorganic materials 0.000 claims description 3
- 229910010848 Li6PS5Cl Inorganic materials 0.000 claims description 3
- 229910009568 Sn0.9Si0.1 Inorganic materials 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910000614 lithium tin phosphorous sulfides (LSPS) Inorganic materials 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052961 molybdenite Inorganic materials 0.000 claims description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 3
- ORQWTLCYLDRDHK-UHFFFAOYSA-N phenylselanylbenzene Chemical compound C=1C=CC=CC=1[Se]C1=CC=CC=C1 ORQWTLCYLDRDHK-UHFFFAOYSA-N 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
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- 238000007581 slurry coating method Methods 0.000 claims description 2
- 239000012780 transparent material Substances 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 claims 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims 2
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a novel battery based on a sulfide solid electrolyte, comprising: the novel battery comprises a negative electrode and a positive electrode in sequence: the solid interface structure comprises a non-solid cathode, a solid interface protective layer, a solid electrolyte, a solid interface protective layer and a non-solid anode; the solid electrolyte is a solid electrolyte taking sulfide as a lithium conducting core and comprises sulfide and a polymer matrix; the polymer matrix accounts for 0-50% of the solid electrolyte by mass.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a novel battery based on sulfide solid electrolyte.
Background
Conventional commercial lithium secondary batteries mostly use liquid electrolytes. However, the energy density of the composite material faces an upper limit bottleneck of 350Wh/kg, and the composite material has safety hazards such as high-temperature thermal runaway and the like. However, compared with flammable organic liquid electrolytes, solid electrolytes have the characteristics of high thermal stability, nonflammability, no leakage, no volatilization and the like, and are beneficial to improving the safety and stability of batteries. Meanwhile, the use of solid electrolyte makes the application of lithium metal negative electrode possible, thereby improving the energy density of the battery, so that the research on the solid electrolyte is a hot spot in the present and future.
The solid electrolyte system mainly comprises three types of polymers, oxides and sulfides, wherein the sulfide solid electrolyte has the advantages of highest ionic conductivity, better mechanical ductility and the like, and is one of the very promising technical routes for developing all-solid-state lithium batteries. The japan new energy industry technology integrated development agency (NEDO) forecasts the future energy storage technology in 2018, which considers that sulfide all-solid-state batteries will occupy 50% of the power battery market in 2025, and reach 90% or more in 2030.
However, recent studies have shown that the high mechanical strength of the solid electrolyte is not completely effective in suppressing lithium dendrites, which are still generated in the sulfide electrolyte when a metallic lithium negative electrode is used, so that the all-solid battery faces problems of large interfacial resistance, short cycle life, and small critical current density. In addition, solid-solid contact between the sulfide electrolyte and the solid positive and negative electrodes is continuously deteriorated, and interface stability is continuously deteriorated, further hindering practical application of the all-solid battery. In order to solve these problems, researchers improve solid-solid contact and inhibit diffusion of lithium dendrites in the electrolyte by optimizing the composition of the sulfide solid electrolyte and forming an artificial electrolyte layer at the interface, and the like.
For example, in the patent application CN111435755A, a sulfide solid-state battery and a method for manufacturing the same, a polymer protective layer with 1% -3% sulfide electrolyte added between a lithium negative electrode and the sulfide electrolyte is proposed, which prolongs the cycle life of the battery to a certain extent, but the symmetric battery has faster increase of polarization voltage and rapidly increased interface impedance, because the traditional solid positive and negative electrodes are used, the problem of unstable solid-solid interface is not solved fundamentally.
For another example, patent application CN112018458A sulfide-polymer composite solid electrolyte, and its preparation method and application propose a method for compounding sulfide solid electrolyte with polymer solid electrolyte in an aqueous solution solvent system, but its sulfide electrolyte has instability in polar organic liquid, which limits its performance and application.
For another example, patent application CN105098140B liquid metal negative electrode material, room temperature liquid metal battery, preparation method and application propose various battery designs using liquid positive and negative electrodes, including cylindrical battery, double flow battery, single flow battery, flat battery, etc., but most of these batteries are complex in structure, and the electrolyte used is Na- β -Al2O3In order to adapt to the cylindrical battery, the ceramic needs to be prepared into a tubular electrolyte by a complex process, and the process is complex and difficult to realize.
In summary, based on the current battery structure system, the instability of the interface between the sulfide electrolyte and the solid anode and cathode always exists, and the problem is difficult to be solved fundamentally. Therefore, a battery system with a sulfide electrolyte as a core lithium conducting layer is facing a great challenge, and a technical means is urgently needed to be found to break through the inherent limitations of the existing liquid lithium battery and solid lithium battery.
Disclosure of Invention
The embodiment of the invention provides a novel battery based on a sulfide solid electrolyte, and provides a novel battery structure, which can solve the problems of poor contact and unstable interface between the sulfide electrolyte and a solid anode and a solid cathode in a traditional battery system, and can reduce interface impedance and prolong the cycle life of the battery.
To this end, embodiments of the present invention provide a novel battery based on a sulfide solid electrolyte,
the novel battery comprises a negative electrode and a positive electrode in sequence: the solid interface structure comprises a non-solid cathode, a solid interface protective layer, a solid electrolyte, a solid interface protective layer and a non-solid anode;
the solid electrolyte is a solid electrolyte taking sulfide as a lithium conducting core and comprises sulfide and a polymer matrix; the polymer matrix accounts for 0-50% of the solid electrolyte by mass.
Preferably, the solid electrolyte is in the shape of a film or a sheet, and the room-temperature ionic conductivity of the solid electrolyte is more than 0.5 mS/cm;
the sulfide includes: li3PS4、Li10GeP2S12、Li7P3S11、Li6PS5Cl、Li9.54Si1.74P1.44S11.7Cl0.3、Li4SnS4、Li3.85Sn0.85Sb0.15S4、Li3.8Sn0.8As0.2S4、Li4Sn0.9Si0.1S4、Li10SnP2S12、Li7GePS8、Li3.25Ge0.25P0.75S4、Li3.25P0.95S4、Li11Si2PS12、Li7P2S8I、Li8P2S9、80(0.7Li2S·0.3P2S5)·20LiI、95(0.8Li2S·0.2P2S5)·5LiI、56Li2S·24P2S5·20Li2O、75Li2S·21P2S5·4P2O5、33(0.7B2S3·0.3P2S5)·67Li2S、67(0.75Li2S·0.25P2S5)·33LiBH4Any one or more of them;
the polymer matrix includes: a polymer containing an ether oxygen group.
Preferably, the non-solid negative electrode is in a liquid state or a gel state;
the liquid non-solid negative electrode is prepared by mixing metal lithium, biphenyl and/or derivatives thereof and ether electrolyte; wherein the ether electrolyte comprises one or more of diethyl ether, methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, tetrahydrofuran, 1, 3-dioxolane, dipropyl ether, diisopropyl ether, ethylbutyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, 2-methyltetrahydrofuran, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxypropane, dioxolane, 1, 4-dioxane, ethylene oxide, propylene oxide and 1, 1-diethoxyethane;
the gel-state non-solid negative electrode is prepared by adding a polymer into the liquid-state non-solid negative electrode to gelatinize the liquid-state non-solid negative electrode; wherein the polymer is one or more of polyethylene oxide (PEO), Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA) and polyvinylidene fluoride (PVDF);
the room-temperature electronic conductivity of the non-solid negative electrode is not lower than 6mS/cm, and the room-temperature ionic conductivity of the non-solid negative electrode is not lower than 3 mS/cm.
Preferably, the non-solid positive electrode is in a liquid state or a gel state;
the liquid non-solid positive electrode specifically comprises: the electrolyte is a liquid which takes any one of organic polysulfide, cyclohexanone and anthraquinone or derivatives thereof as solute, and ether or carbonate organic liquid electrolyte as solvent, and contains lithium salt and conductive additive;
wherein the organic polysulfide comprises: one or more of diphenyl polysulfide, dimethyl polysulfide, pyridyl polysulfide, and diphenyl selenide sulfide;
the ether organic liquid electrolyte comprises: one or more of diethyl ether, methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, tetrahydrofuran, 1, 3-dioxolane, dipropyl ether, diisopropyl ether, ethylbutyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, 2-methyltetrahydrofuran, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxypropane, dioxolane, 1, 4-dioxane, ethylene oxide, propylene oxide and 1, 1-diethoxyethane;
the carbonate-based organic liquid electrolyte includes: one or more of ethylene carbonate, diethyl carbonate, propylene carbonate and dimethyl carbonate;
the lithium salt includes: lithium bis (trifluoromethylsulfonyl) imide LiTFSI, lithium bis (fluorosulfonyl) imide LiFSI, lithium triflate LiTof, lithium hexafluorophosphate LiPF6Lithium tetrafluoroborate (LiBF)4Lithium perchlorate LiClO4One or more of;
the conductive additive includes: one or more of vapor grown carbon fiber VGCF, conductive carbon black Super P and multi-walled carbon nanotube MWCNT;
the gel-state non-solid positive electrode is prepared by adding a polymer into the liquid-state non-solid positive electrode to gelatinize the liquid-state non-solid positive electrode; wherein the polymer is one or more of polyethylene oxide (PEO), Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA) and polyvinylidene fluoride (PVDF).
Preferably, the thickness of the solid interface protective layer is 0.5-200 microns, and the solid interface protective layer is a polymer protective layer or a sulfide protective layer;
the polymer protective layer is specifically a polymer added with lithium salt; the mass ratio of the polymer to the lithium salt is 1: 10-10: 1; wherein the polymer specifically comprises: one or more of polyethylene oxide (PEO), polypropylene oxide (PPO), polymethyl methacrylate (PMMA), Polyacrylonitrile (PAN) and polyvinylidene fluoride (PVDF); the lithium salt includes: lithium bis (trifluoromethylsulfonyl) imide LiTFSI, lithium bis (fluorosulfonyl) imide LiFSI, lithium triflate LiTof, lithium hexafluorophosphate LiPF6Lithium tetrafluoroborate (LiBF)4Lithium perchlorate LiClO4One or more of;
the material component of the sulfide protective layer is beta-Li3PS4、MoS2、CuS、Li2And S has a crystal structure of crystal or amorphous.
Preferably, the solid interface protective layer is prepared on both surfaces of the solid electrolyte by means of slurry coating, or the solid electrolyte is immersed in a slurry of the solid interface protective layer, and then is subjected to pulling and drying for a plurality of times, so that the solid interface protective layer is prepared on both surfaces of the solid electrolyte.
Preferably, the novel battery further comprises a positive electrode liquid storage cavity and a negative electrode liquid storage cavity;
the solid electrolyte with solid interface protective layers on the surfaces of two sides is arranged between the anode liquid storage cavity and the cathode liquid storage cavity and is hermetically connected with the anode liquid storage cavity and the cathode liquid storage cavity through the shell, the non-solid anode is in contact with the solid interface protective layer on one side of the solid electrolyte through the anode liquid storage cavity, and the non-solid cathode is in contact with the solid interface protective layer on the other side of the solid electrolyte through the cathode liquid storage cavity.
Further preferably, the positive electrode liquid storage cavity, the negative electrode liquid storage cavity and the shell are all made of transparent materials.
Preferably, the novel battery further comprises a metallic lithium sheet disposed in the non-solid negative electrode.
The novel battery based on the sulfide solid electrolyte provided by the embodiment of the invention sequentially comprises the following structures from a negative electrode to a positive electrode: the solid interface structure comprises a non-solid cathode, a solid interface protective layer, a solid electrolyte, a solid interface protective layer and a non-solid anode; by introducing the non-solid positive electrode and the non-solid negative electrode, the problems of poor contact and unstable interface between the sulfide electrolyte and the solid positive electrode and the solid negative electrode in the traditional battery system can be solved; the non-solid negative electrode has excellent lithium-dissolving performance, so that solid lithium dendrites are dissolved in a solvent contained in the non-solid negative electrode, and nucleation and growth of the lithium dendrites are fundamentally inhibited; the sulfide solid electrolyte is modified, so that the sulfide solid electrolyte has excellent ionic conductivity and simultaneously has flexibility and compactness; the surface protection is carried out on the sulfide solid electrolyte through the solid interface protection layer, so that the solid electrolyte is compatible and stable with non-solid anode and cathode materials, and the physical contact and the electrochemical reaction of the interface between the non-solid electrode and the solid electrolyte are isolated, so that the interface impedance is reduced, and the cycle life of the battery is prolonged. The novel battery based on the sulfide solid electrolyte has a novel battery structure, the non-solid positive and negative electrodes are in close interface contact with the sulfide solid electrolyte, so that good ion migration and transportation are ensured, and meanwhile, the structure has excellent sealing performance, and the possibility of denaturation of a sulfide solid electrolyte material caused by air infiltration is eliminated.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
Fig. 1 is a structural diagram of a novel sulfide solid electrolyte-based battery provided by an embodiment of the present invention;
fig. 2 is a physical diagram of a novel sulfide solid electrolyte-based battery provided by an embodiment of the invention;
fig. 3 is full battery charge-discharge cycle data provided in example 1 of the present invention and comparative example 1;
FIG. 4 is a view of coating of beta-Li as provided in example 2 of the present invention3PS4A sulfide electrolyte sheet of the protective layer;
fig. 5 shows the polarization voltage test results of the symmetrical cell provided in example 2 of the present invention;
figure 6 is a sheet of sulfide electrolyte coated with a PEO protective layer as provided in example 3 of the present invention;
fig. 7 shows the polarization voltage test results of the symmetrical cell provided in example 3 of the present invention;
fig. 8 is a sulfide-polymer composite electrolyte sheet of a magnetron-sputtered LiPON protective layer provided in embodiment 4 of the present invention;
fig. 9 shows the polarization voltage test results of the symmetrical cell provided in example 4 of the present invention;
fig. 10 is a sulfide electrolyte sheet with a LiF protective layer provided in example 5 of the present invention;
fig. 11 shows the polarization voltage test results of the symmetrical cell provided in example 5 of the present invention;
FIG. 12 is a comparison of electrochemical cycle data of examples 2, 3, 4, 5 and 2 according to the present invention;
fig. 13 is a comparison graph of the voltage and current density test results of eight symmetrical batteries with different solid interface protective layers provided in example 6 of the present invention;
fig. 14 is a graph of voltage versus cycle time for eight symmetrical cells with different solid interfacial protection layers, as provided in example 6 of the present invention;
fig. 15 is a graph of current density versus cycle time for eight symmetrical batteries with different solid interface protective layers, as provided in example 6 of the present invention;
fig. 16 is a comparison graph of the limiting current densities of eight symmetrical batteries with different solid interface protective layers provided in example 6 of the present invention;
fig. 17 is a graph comparing the critical unit area capacity of eight symmetrical batteries with different solid interfacial protection layers according to example 6 of the present invention;
fig. 18 is a plot of limiting current density and critical unit area capacity for a variety of symmetrical cells, as reported in the present invention and the literature.
Detailed Description
The invention is further illustrated by the following figures and specific examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as in any way limiting the present invention, i.e., as in no way limiting its scope.
The invention provides a novel battery based on a sulfide solid electrolyte, which sequentially comprises the following components from a negative electrode to a positive electrode: the solid interface structure comprises a non-solid cathode, a solid interface protective layer, a solid electrolyte, a solid interface protective layer and a non-solid anode; in a preferred scheme, a metal lithium sheet can be further included, and the metal lithium sheet is arranged in the non-solid negative electrode.
Fig. 1 shows a specific implementation scheme of the novel battery based on a sulfide solid electrolyte according to the present invention, and as shown in fig. 1, the novel battery sequentially includes, from a negative electrode to a positive electrode: a non-solid negative electrode 1, a solid interface protective layer 2-1, a solid electrolyte 3, a solid interface protective layer 2-2 and a non-solid positive electrode 4. The embodiments are based on the battery model, which is not intended to limit the invention, and any modification, equivalent replacement, and improvement made within the design spirit of the invention should be included in the scope of the invention.
The solid electrolyte is a solid electrolyte taking sulfide as a lithium-conducting core, and comprises sulfide and a polymer matrix; the polymer matrix accounts for 0-50% of the solid electrolyte by mass.
The solid electrolyte is in a shape of a film or a sheet, and the room-temperature ionic conductivity of the solid electrolyte is more than 0.5 mS/cm;
the sulfide includes: li3PS4、Li10GeP2S12、Li7P3S11、Li6PS5Cl、Li9.54Si1.74P1.44S11.7Cl0.3、Li4SnS4、Li3.85Sn0.85Sb0.15S4、Li3.8Sn0.8As0.2S4、Li4Sn0.9Si0.1S4、Li10SnP2S12、Li7GePS8、Li3.25Ge0.25P0.75S4、Li3.25P0.95S4、Li11Si2PS12、Li7P2S8I、Li8P2S9、80(0.7Li2S·0.3P2S5)·20LiI、95(0.8Li2S·0.2P2S5)·5LiI、56Li2S·24P2S5·20Li2O、75Li2S·21P2S5·4P2O5、33(0.7B2S3·0.3P2S5)·67Li2S、67(0.75Li2S·0.25P2S5)·33LiBH4Any one or more of them;
the polymer matrix is a polymer containing an ether oxygen group.
The thickness of the solid interface protective layer is 0.5-200 microns, and the solid interface protective layer is specifically a polymer protective layer or a sulfide protective layer;
the polymer protective layer is specifically a polymer added with lithium salt; the mass ratio of the polymer to the lithium salt is 1: 10-10: 1; wherein the polymer specifically comprises: one or more of polyethylene oxide (PEO), polypropylene oxide (PPO), polymethyl methacrylate (PMMA), Polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF); the lithium salt includes: lithium bistrifluoromethylsulfonyl imide (LiTFSI), lithium bistrifluorosulfonimide (LiFSI), lithium trifluoromethanesulfonate (lituf), lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium perchlorate (LiClO)4) One or more of;
the material component of the sulfide protective layer is beta-Li3PS4、MoS2、CuS、Li2And S has a crystal structure of crystal or amorphous.
And preparing the solid interface protective layers on the two side surfaces of the solid electrolyte in a homogenate coating mode, or soaking the solid electrolyte into slurry of the solid interface protective layers, and then carrying out pulling and drying for multiple times, thereby preparing the solid interface protective layers on the two side surfaces of the solid electrolyte.
The polymer or sulfide protective layer used for the above solid interface protective layer is insoluble in the organic liquid electrolyte of the following non-solid positive electrode or non-solid negative electrode.
The non-solid negative electrode is in a liquid state or a gel state.
The liquid non-solid negative electrode is prepared by mixing metal lithium, biphenyl and/or derivatives thereof and ether electrolyte; the molar ratio of the metal lithium, the biphenyl and/or the derivatives thereof and the ether electrolyte is preferably (0.1-3.0): (0.5-5.0): 10. wherein the ether electrolyte comprises one or more of diethyl ether, methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, tetrahydrofuran, 1, 3-dioxolane, dipropyl ether, diisopropyl ether, ethylbutyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, 2-methyltetrahydrofuran, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxypropane, dioxolane, 1, 4-dioxane, ethylene oxide, propylene oxide and 1, 1-diethoxyethane;
the gel-state non-solid negative electrode is prepared by adding a polymer into the liquid-state non-solid negative electrode to gelatinize the liquid-state non-solid negative electrode; wherein the polymer comprises one or more of polyethylene oxide (PEO), Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF); adding a non-solid negative electrode in a liquid state by mass ratio: polymer 1: (0.01-0.1).
The room-temperature electronic conductivity of the non-solid negative electrode is not less than 6mS/cm, and the room-temperature ionic conductivity is not less than 3 mS/cm.
The non-solid positive electrode is in a liquid state or a gel state.
The liquid non-solid positive electrode is specifically as follows: the electrolyte is a liquid which takes any one of organic polysulfide, cyclohexanone and anthraquinone or derivatives thereof as solute, and ether or carbonate organic liquid electrolyte as solvent, and contains lithium salt and conductive additive; wherein the addition concentration of the lithium salt is 0.1-2 mol/L; the addition amount of the conductive additive is 100mg-1000mg added in each 10ml of the non-solid positive electrode.
Organic polysulfides include: one or more of diphenyl polysulfide, dimethyl polysulfide, pyridyl polysulfide, and diphenyl selenide sulfide;
the ether organic liquid electrolyte comprises: one or more of diethyl ether, methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, tetrahydrofuran, 1, 3-dioxolane, dipropyl ether, diisopropyl ether, ethylbutyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, 2-methyltetrahydrofuran, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxypropane, dioxolane, 1, 4-dioxane, ethylene oxide, propylene oxide and 1, 1-diethoxyethane;
the carbonate-based organic liquid electrolyte includes: one or more of ethylene carbonate, diethyl carbonate, propylene carbonate and dimethyl carbonate;
the lithium salt includes: lithium bistrifluoromethylsulfonyl imide (LiTFSI), lithium bistrifluorosulfonimide (LiFSI), lithium trifluoromethanesulfonate (lituf), lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium perchlorate (LiClO)4) One or more of;
the conductive additive includes: one or more of Vapor Grown Carbon Fiber (VGCF), conductive carbon black (Super P), multi-walled carbon nanotube (MWCNT);
the gel-state non-solid positive electrode is prepared by adding a polymer into a liquid non-solid positive electrode to gelatinize the liquid non-solid positive electrode; wherein the polymer comprises one or more of polyethylene oxide (PEO), Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF).
The novel battery also comprises a positive electrode liquid storage cavity and a negative electrode liquid storage cavity; shown as marks 5 and 6, respectively, in fig. 1.
The solid electrolyte with solid interface protective layers on the surfaces of two sides is arranged between the anode liquid storage cavity and the cathode liquid storage cavity and is hermetically connected with the anode liquid storage cavity through the shell, the non-solid anode is contacted with the solid interface protective layer on one side of the solid electrolyte through the anode liquid storage cavity, and the non-solid cathode is contacted with the solid interface protective layer on the other side of the solid electrolyte through the cathode liquid storage cavity.
The novel battery based on the sulfide solid electrolyte provided by the embodiment of the invention sequentially comprises the following structures from a negative electrode to a positive electrode: the solid interface structure comprises a non-solid cathode, a solid interface protective layer, a solid electrolyte, a solid interface protective layer and a non-solid anode; by introducing the non-solid positive electrode and the non-solid negative electrode, the problems of poor contact and unstable interface between the sulfide electrolyte and the solid positive electrode and the solid negative electrode in the traditional battery system can be solved; the non-solid negative electrode has excellent lithium-dissolving performance, so that solid lithium dendrites are dissolved in a solvent contained in the non-solid negative electrode, and nucleation and growth of the lithium dendrites are fundamentally inhibited; in the following specific examples of the invention, it is preferred to use a Li-Bp-DME system liquid anode that can dissolve metallic lithium and has good electronic and ionic conductivity, very similar properties to metallic lithium anodes, and can be used as a "lithium source" for lithium cyclic de-intercalation due to its excellent electronic and ionic conductivity. The sulfide solid electrolyte is modified, so that the solid electrolyte has excellent ionic conductivity and simultaneously has flexibility and compactness; the surface protection is carried out on the sulfide solid electrolyte through the solid interface protection layer, so that the solid electrolyte is compatible and stable with non-solid anode and cathode materials, and the physical contact and the electrochemical reaction of the interface between the non-solid electrode and the solid electrolyte are isolated, so that the interface impedance is reduced, and the cycle life of the battery is prolonged. The novel battery based on the sulfide solid electrolyte has a novel battery structure, the non-solid positive and negative electrodes are in close interface contact with the sulfide solid electrolyte, so that good ion migration and transportation are ensured, and meanwhile, the structure has excellent sealing performance, and the possibility of denaturation of a sulfide solid electrolyte material caused by air infiltration is eliminated.
In order to better understand the technical solutions provided by the present invention, the following description will respectively illustrate the specific implementation and performance characteristics of the novel sulfide solid electrolyte-based battery provided by the above embodiments of the present invention with several specific examples.
Example 1
Li is selected for this example7P3S11As solid electrolytes, beta-Li3PS4The method is a solid interface protection layer material, Li-Bp-DME solution is a liquid negative electrode, anthraquinone is a liquid positive electrode, a battery model shown in figure 1 is taken as a basis, a lithium metal sheet is arranged on a stainless steel current collector on the negative electrode side of the battery model, and a full battery is assembled by the following specific implementation steps:
1. taking Li2S and S were dissolved in Tetrahydrofuran (THF) to give solution 1. Taking Li2S and P2S5Dissolving in Acetonitrile (ACN) to obtain a solution 2, and then mixing the solution 1 and the solution 2 to obtain a precursor solution.
2. Taking Li7P3S11The electrolyte sheet having a diameter of 15mm and a thickness of 0.7mm was obtained by tabletting, and its ionic conductivity was measured to be 0.5944 mS/cm. Pulling the electrolyte sheet in the precursor solution for 10 times, and then carrying out heat treatment at 230 ℃ for 1 hour to form beta-Li on the surface3PS4Li of solid interface protective layer7P3S11An electrolyte sheet.
3. Adding Anthraquinone (AQ), LiTFSI and a conductive additive SP into Propylene Carbonate (PC), and stirring at normal temperature for 1 hour to obtain a black and viscous positive liquid;
4. biphenyl (BP) is dissolved in 6ml ethylene glycol dimethyl ether (DME) to form a transparent BP-DME solution, lithium filaments are dissolved in the BP-DME solution to form blue-black Li1.5BP3DME10A negative electrode liquid;
5. using the battery model of this patent, the intermediate clamping surface had beta-Li3PS4Li of solid interface protective layer7P3S11Electrolyte sheet, 5ml Li is injected into two sides of battery1.5BP3DME10The whole battery is assembled by the cathode liquid and 5ml of the anode liquid; the full-cell real beat diagram is shown in fig. 2.
6. Full cell charge-discharge cycle data was obtained using a blue test at a rate of 0.1C, as shown in fig. 3-1.
Comparative example 1
Li is selected for this example7P3S11As a solid electrolyte, a non-interface protection layer material, Li-Bp-DME solution as a liquid negative electrode, anthraquinone as a liquid positive electrode, and based on the battery model shown in figure 1, a lithium metal sheet is arranged on a stainless steel current collector at the negative electrode side, and a full battery is assembled, and the specific implementation steps are as follows:
1. adding Anthraquinone (AQ), LiTFSI and a conductive additive SP into Propylene Carbonate (PC), and stirring at normal temperature for 1 hour to obtain a black and viscous positive liquid;
2. taking Li7P3S11The electrolyte sheet having a diameter of 15mm and a thickness of 0.7mm was obtained by tabletting, and its ionic conductivity was measured to be 0.6369 mS/cm.
3. Biphenyl (BP) is dissolved in 6ml ethylene glycol dimethyl ether (DME) to form a transparent BP-DME solution, lithium filaments are dissolved in the BP-DME solution to form blue-black Li1.5BP3DME10A negative electrode liquid;
4. using the battery model in this patent, Li was sandwiched between7P3S11Electrolyte sheet, 5ml Li is injected into two sides of battery1.5BP3DME10And 5ml of the positive electrode liquid were assembled into a full cell.
5. Full cell charge-discharge cycle data were obtained using a blue test at a rate of 0.1C, as shown in fig. 3-2.
Anthraquinone, as a representative of organic carbonyl compound electrode materials, has the advantages of long cycle life and low cost. As can be seen from FIG. 3-1, when the electrolyte is used as a liquid anode and an interface protective layer material is used, the initial capacity reaches 230mAh/g, and the electrolyte can still maintain the capacity of 150mAh/g after 16 cycles of circulation, and the circulation stability is good. As can be seen from fig. 3-2, the full battery capacity without using the interface protection layer material decays rapidly, which illustrates that the interface protection layer technology proposed by the present invention has a significant improvement effect on the full battery performance.
Example 2
Li is selected for this example7P3S11As solid electrolytes, beta-Li3PS4The method is a solid interface protective layer material, Li-Bp-DME solution is a liquid negative electrode, a symmetrical battery is assembled by using a battery model shown in FIG. 1, and the specific implementation steps are as follows:
1. li2S and S were dissolved in Tetrahydrofuran (THF) to give solution 1. Dissolving Li2S and P2S5 in Acetonitrile (ACN) to obtain a solution 2, and then mixing the solution 1 and the solution 2 to obtain a precursor solution.
2. Taking Li7P3S11The electrolyte sheet having a diameter of 15mm and a thickness of 0.7mm was obtained by tabletting, and its ionic conductivity was measured to be 0.5944 mS/cm. Pulling the electrolyte sheet in the precursor solution for 10 times, and then carrying out heat treatment at 230 ℃ for 1 hour to form beta-Li on the surface3PS4Li of solid interface protective layer7P3S11ElectrolyteSlicing; the electrolyte sheet was photographed as shown in figure 4.
3. Dissolving Biphenyl (BP) in ethylene glycol dimethyl ether (DME) to form a transparent BP-DME solution, dissolving lithium filaments in the BP-DME solution to form blue-black Li1.5BP3DME10A negative electrode liquid;
4. using the battery model of this patent, the middle clamping surface has beta-Li3PS4Li of solid interface protective layer7P3S11Electrolyte sheet, 5ml Li injected on both sides of battery1.5BP3DME10Assembling a lithium symmetric battery by using the negative electrode liquid; the test of the blue electric system at 30 ℃ obtains symmetrical battery cycle data, and the current density is 0.127mA/cm2As shown in fig. 5.
According to the test, the initial polarization voltage is smaller and is 0.1V, and after 200 hours of circulation, the polarization voltage is increased by about 0.025V compared with the initial polarization voltage, which indicates that the polarization voltage is based on beta-Li3PS4The novel battery of the solid interface protective layer material realizes lower interface impedance and better cycle stability.
beta-Li as an option in this example3PS4Is a material which is stable to organic solution in a sulfide electrolyte system because of PS in the structure4 3-Tetrahedra and Li+The bonding is strong, so the composite material is not easy to dissolve in organic solution, and can be used as a good interface protective layer to isolate the interface physical contact between the non-solid electrode and the sulfide solid electrolyte and inhibit the interface chemical reaction.
Example 3
Li is selected for this example7P3S11As a solid electrolyte, PEO doped with lithium salt LiTFSI is a solid interface protective layer material, Li-Bp-DME solution is a liquid negative electrode, and a symmetrical battery is assembled by using a battery model shown in FIG. 1, and the specific implementation steps are as follows:
1. dissolving PEO and LiTFSI in Acetonitrile (ACN), and stirring at 25 deg.C until completely dissolved to form uniform slurry;
2. taking Li7P3S11Tabletting to obtain electrolyte sheet with diameter of 15mm and thickness of 0.7mmThe ionic conductivity was measured to be 0.5944 mS/cm. Dripping the slurry obtained in the step 1 on the two side surfaces of the electrolytic sheet, uniformly coating, baking and drying on a heating table at 200 ℃ to form Li doped with lithium salt LiTFSI (polyethylene oxide) with PEO as a solid interface protective layer material7P3S11An electrolyte sheet; as shown in fig. 6.
3. Dissolving Biphenyl (BP) in ethylene glycol dimethyl ether (DME) to form a transparent BP-DME solution, dissolving lithium filaments in the BP-DME solution to form blue-black Li1.5BP3DME10A negative electrode liquid;
4. li with PEO doped with lithium salt LiTFSI sandwiched between battery models in the patent as solid interface protective layer material7P3S11Electrolyte sheet, both sides of the cell were impregnated with 5ml Li1.5BP3DME10Assembling a lithium symmetric battery by using the negative electrode liquid;
5. symmetric cell cycle data, 0.127mA/cm, were obtained using a blue test system at 25 deg.C2As shown in fig. 7.
According to the test, the initial polarization voltage is larger, but rapidly decreases, which indicates that the PEO interface protective layer is activated rapidly, and the polarization voltage is stabilized at 0.15V rapidly and does not increase within 170 h. At this time, the test temperature was raised to 30 ℃, the polarization voltage was rapidly decreased to 0.12V, and a very stable state was maintained for the next 210 hours.
The PEO selected for this example is one of the common materials used to stabilize the solid-solid contact interface in conventional all-solid batteries, and in this example was found to still isolate the non-solid electrode from the interfacial physical contact with the sulfide solid electrolyte, and to have an activation process that helps achieve lower interfacial resistance and better cycling stability.
Example 4
Li is selected for this example7P3S11A sulfide electrolyte and a PEO polymer matrix are used for preparing a composite solid electrolyte material, LiPON is a solid interface protection layer material, Li-Bp-DME solution is a liquid negative electrode, a symmetrical battery is assembled by using a battery model shown in FIG. 1, and the specific implementation steps are as follows:
1. taking Li2S、P2S5Weighing and adding the mixture into acetonitrile according to the molar ratio of 7:3, and uniformly stirring at normal temperature to obtain slurry A; PEO and LiTFSI are weighed according to the molar ratio of 8: 1 and evenly stirred in acetonitrile to obtain slurry B. And mixing the slurry A and the slurry B according to the proportion that the sulfide electrolyte accounts for 80% of the total mass of the composite electrolyte to obtain slurry C. And (3) placing the slurry C in a heating table for drying, and then carrying out high-temperature treatment in a muffle furnace to obtain the composite electrolyte material. The composite electrolyte material is taken to be pressed into a sheet, and an electrolyte sheet with the diameter of 15mm and the thickness of 0.7mm is obtained.
2. 2-micron LiPON is respectively plated on the two sides of the composite solid electrolyte sheet by a magnetron sputtering method, and the photo of the plated film is shown in figure 8;
3. the battery model is used, a composite electrolyte sheet plated with a LiPON solid interface protective layer material is clamped in the middle, and 5ml of Li is injected into two sides of the battery1.5BP3DME10Assembling a lithium symmetric battery by using the negative electrode liquid;
4. symmetric cell cycle data were obtained using a blue test system at 30 ℃ with a current density of 0.127mA/cm2As shown in fig. 9. The initial polarization voltage of the symmetrical cell was 0.53V, increasing to 0.86V after 170 hours of cycling.
Example 5
Li is selected for this example7P3S11As a solid electrolyte, LiF is a solid interface protective layer material, Li-Bp-DME solution is a liquid cathode, and a symmetrical battery is assembled by using the battery model shown in FIG. 1, and the specific implementation steps are as follows:
1. 0.15g of Li was taken7P3S11Tabletting to obtain an electrolyte sheet with the diameter of 15mm and the thickness of 0.7mm, wherein the ionic conductivity of the electrolyte sheet is 0.9 mS/cm;
2. adding a small amount of LiTFSI into 1ml DME step by step, and stirring for 10 hours to obtain a LiTFSI (DME) solution with the concentration of 6 mol/L;
3. and (3) flatly placing the lithium sheet, dropwise adding a plurality of drops of the solution on the surface of the lithium sheet by using a liquid transfer gun, then placing an electrolyte sheet, dropwise adding a plurality of drops of the solution on the surface of the electrolyte by using the liquid transfer gun, and then placing another lithium sheet. After standing at 120 ℃ for 12 hours, the lithium sheets on both sides were removed to obtain an electrolyte sheet having a LiF solid interface protective layer as shown in fig. 10.
4. Li coated with LiF solid interface protective layer material by using the battery model of the patent7P3S11Electrolyte sheet, both sides of the cell were impregnated with 5ml Li1.5BP3DME10Assembling a lithium symmetric battery by using the negative electrode liquid;
5. symmetric cell cycle data were obtained using a blue test system at 30 ℃ with a current density of 0.127mA/cm2As shown in fig. 11. The initial polarization voltage of the symmetrical cell was 0.13V, and the increase was 0.34V after 110 hours of cycling.
Comparative example 2
Li was used as the comparative example7P3S11As a solid electrolyte, a material without an interface protection layer and Li-Bp-DME solution as a liquid negative electrode, a symmetrical battery is assembled by using a battery model shown in FIG. 1, and the specific implementation steps are as follows:
1. taking Li7P3S11Tabletting to obtain an electrolyte sheet with the diameter of 15mm and the thickness of 0.7mm, wherein the ionic conductivity of the electrolyte sheet is 0.6 mS/cm;
2. li with battery model and without interface protective layer material clamped in middle7P3S11Electrolyte sheet, both sides of the cell were impregnated with 5ml Li1.5BP3DME10Assembling a lithium symmetric battery by using the negative electrode liquid;
3. cycling data was obtained using a blue test system at 30 ℃ for a symmetrical cell with a current density of 0.127mA/cm2, an initial polarization voltage of 0.55V, and an increase to 1.5V after 350 hours of cycling.
The cycle data of example 2, example 3, example 4, example 5 and comparative example 2 were compared together as shown in fig. 12. Illustrating the significant reduction in the polarization voltage of the cell after interfacial protection of the sulfide electrolyte sheet, with the beta-Li used in example 23PS4And the PEO interface protective layer used in example 3 had the most excellent protective effect.
Example 6
Li is selected for this example7P3S11As solid electrolyte, 8 different solid interface protective layers were used, respectively: PEO interfacial protection layers of 4 different thicknesses were prepared using the method of example 3, wt (PEO) wt (LiTFSI) 3:2 in the homogenate, and the volumes of the homogenate instilled on the side of the electrolyte sheet were 20. mu.l, 30. mu.l, 40. mu.l and 50. mu.l, respectively; 4 different thicknesses of beta-Li were prepared using the method of example 23PS4An interface protective layer formed by separately adding Li7P3S11The sheets were pulled 10 times, 20 times, 40 times, and 80 times in the dark brown precursor solution.
In order to show the good performance of the novel battery for inhibiting lithium dendrite, the electrolyte with the 8 solid interface protective layers is assembled into a symmetrical battery respectively, and the limiting current density and the critical unit area capacity of the symmetrical battery are measured. The specific operation is as follows:
1. taking Li7P3S11Tabletting to obtain electrolyte sheet with diameter of 15mm and thickness of 0.7mm, and preparing Li with 8 interface protective layer materials according to the above method7P3S11An electrolyte sheet.
2. The Li with the 8 solid interface protective layers is clamped in the middle by using the battery model7P3S11Electrolyte sheet, both sides of the cell were impregnated with 5ml Li1.5BP3DME10And assembling the lithium-lithium symmetrical battery by using the negative electrode liquid, and preparing a symmetrical battery without the solid interface protective layer.
3. At 30 ℃, all the symmetrical batteries are subjected to charge-discharge cycle test under the current which starts to be increased step by step at the current of 0.2mA, and the step length of each step is 0.25mA until short circuit occurs or the voltage reaches the safe voltage of a detection instrument.
Results of voltage and current density tests on eight symmetric cells with different solid interface protective layers are shown in fig. 13, voltage-cycle time on fig. 14, and current density-cycle time on fig. 15.
Can be seen to be based on beta-Li3PS4The symmetrical battery with the PEO solid interface protective layer generally realizes high limiting current densityAnd (4) degree. In 4 kinds of beta-Li3PS4In the solid interface protection layer, the interface protection effect is the best when the interface is pulled for 80 times; of the 4 PEO solid interfacial layer, an interfacial protection effect of 30. mu.l volume of homogenate applied was the best.
The specific values of the limiting current density and critical unit area capacity of eight batteries with solid interface protection layers plus one without solid interface protection layer are summarized as shown in fig. 16 and 17, respectively.
Therefore, based on the novel battery structure provided by the invention, the limit current density of the symmetrical battery is as high as 5.715mA/cm2The critical unit surface capacity is up to 5.715mAh/cm2Such excellent performance is quite rare in prior symmetric battery systems, see fig. 18. This is a good indication that the novel battery technology proposed by the present invention can significantly suppress the formation of lithium dendrites and prolong the cycle life.
According to the novel battery based on the sulfide solid electrolyte provided by the embodiment of the invention, the problems of poor contact and unstable interface between the sulfide electrolyte and the solid positive and negative electrodes in the traditional battery system can be solved by introducing the non-solid positive electrode and the non-solid negative electrode; the non-solid negative electrode has excellent lithium-dissolving performance, so that solid lithium dendrites are dissolved in a solvent contained in the non-solid negative electrode, and nucleation and growth of the lithium dendrites are fundamentally inhibited; the sulfide solid electrolyte is modified, so that the sulfide solid electrolyte has excellent ionic conductivity and simultaneously has flexibility and compactness; the surface protection is carried out on the sulfide solid electrolyte through the solid interface protection layer, so that the solid electrolyte is compatible and stable with non-solid anode and cathode materials, and the physical contact and the electrochemical reaction of the interface between the non-solid electrode and the solid electrolyte are isolated, so that the interface impedance is reduced, and the cycle life of the battery is prolonged. The novel battery based on the sulfide solid electrolyte has a novel battery structure, the non-solid positive and negative electrodes are in close interface contact with the sulfide solid electrolyte, so that good ion migration and transportation are ensured, and meanwhile, the structure has excellent sealing performance, and the possibility of denaturation of a sulfide solid electrolyte material caused by air infiltration is eliminated.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A novel battery based on a sulfide solid electrolyte is characterized in that the novel battery sequentially comprises from a negative electrode to a positive electrode: the solid interface structure comprises a non-solid cathode, a solid interface protective layer, a solid electrolyte, a solid interface protective layer and a non-solid anode;
the solid electrolyte is a solid electrolyte taking sulfide as a lithium conducting core and comprises sulfide and a polymer matrix; the polymer matrix accounts for 0-50% of the solid electrolyte by mass.
2. The novel battery of claim 1, wherein the solid electrolyte is in the form of a film or sheet, and has a room temperature ionic conductivity of greater than 0.5 mS/cm;
the sulfide includes: li3PS4、Li10GeP2S12、Li7P3S11、Li6PS5Cl、Li9.54Si1.74P1.44S11.7Cl0.3、Li4SnS4、Li3.85Sn0.85Sb0.15S4、Li3.8Sn0.8As0.2S4、Li4Sn0.9Si0.1S4、Li10SnP2S12、Li7GePS8、Li3.25Ge0.25P0.75S4、Li3.25P0.95S4、Li11Si2PS12、Li7P2S8I、Li8P2S9、80(0.7Li2S·0.3P2S5)·20LiI、95(0.8Li2S·0.2P2S5)·5LiI、56Li2S·24P2S5·20Li2O、75Li2S·21P2S5·4P2O5、33(0.7B2S3·0.3P2S5)·67Li2S、67(0.75Li2S·0.25P2S5)·33LiBH4Any one or more of them;
the polymer matrix includes: a polymer containing an ether oxygen group.
3. The novel battery of claim 1, wherein the non-solid negative electrode is in a liquid or gel state;
the liquid non-solid negative electrode is prepared by mixing metal lithium, biphenyl and/or derivatives thereof and ether electrolyte; wherein the ether electrolyte comprises one or more of diethyl ether, methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, tetrahydrofuran, 1, 3-dioxolane, dipropyl ether, diisopropyl ether, ethylbutyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, 2-methyltetrahydrofuran, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxypropane, dioxolane, 1, 4-dioxane, ethylene oxide, propylene oxide and 1, 1-diethoxyethane;
the gel-state non-solid negative electrode is prepared by adding a polymer into the liquid-state non-solid negative electrode to gelatinize the liquid-state non-solid negative electrode; wherein the polymer is one or more of polyethylene oxide (PEO), Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA) and polyvinylidene fluoride (PVDF);
the room-temperature electronic conductivity of the non-solid negative electrode is not lower than 6mS/cm, and the room-temperature ionic conductivity of the non-solid negative electrode is not lower than 3 mS/cm.
4. The novel battery of claim 1, wherein the non-solid positive electrode is in a liquid or gel state;
the liquid non-solid positive electrode specifically comprises: the electrolyte is a liquid which takes any one of organic polysulfide, cyclohexanone and anthraquinone or derivatives thereof as solute, and ether or carbonate organic liquid electrolyte as solvent, and contains lithium salt and conductive additive;
wherein the organic polysulfide comprises: one or more of diphenyl polysulfide, dimethyl polysulfide, pyridyl polysulfide, and diphenyl selenide sulfide;
the ether organic liquid electrolyte comprises: one or more of diethyl ether, methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, tetrahydrofuran, 1, 3-dioxolane, dipropyl ether, diisopropyl ether, ethylbutyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, 2-methyltetrahydrofuran, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxypropane, dioxolane, 1, 4-dioxane, ethylene oxide, propylene oxide and 1, 1-diethoxyethane;
the carbonate-based organic liquid electrolyte includes: one or more of ethylene carbonate, diethyl carbonate, propylene carbonate and dimethyl carbonate;
the lithium salt includes: lithium bis (trifluoromethylsulfonyl) imide LiTFSI, lithium bis (fluorosulfonyl) imide LiFSI, lithium triflate LiTof, lithium hexafluorophosphate LiPF6Lithium tetrafluoroborate (LiBF)4Lithium perchlorate LiClO4One or more of;
the conductive additive includes: one or more of vapor grown carbon fiber VGCF, conductive carbon black Super P and multi-walled carbon nanotube MWCNT;
the gel-state non-solid positive electrode is prepared by adding a polymer into the liquid-state non-solid positive electrode to gelatinize the liquid-state non-solid positive electrode; wherein the polymer is one or more of polyethylene oxide (PEO), Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA) and polyvinylidene fluoride (PVDF).
5. The novel battery according to claim 1, wherein the thickness of the solid interface protective layer is 0.5 to 200 μm, in particular a polymer protective layer or a sulfide protective layer;
the polymer protective layer is specifically a polymer added with lithium salt; the mass ratio of the polymer to the lithium salt is 1: 10-10: 1; wherein the polymer specifically comprises: one or more of polyethylene oxide (PEO), polypropylene oxide (PPO), polymethyl methacrylate (PMMA), Polyacrylonitrile (PAN) and polyvinylidene fluoride (PVDF); the lithium salt includes: lithium bis (trifluoromethylsulfonyl) imide LiTFSI, lithium bis (fluorosulfonyl) imide LiFSI, lithium triflate LiTof, lithium hexafluorophosphate LiPF6Lithium tetrafluoroborate (LiBF)4Lithium perchlorate LiClO4One or more of;
the material component of the sulfide protective layer is beta-Li3PS4、MoS2、CuS、Li2And S has a crystal structure of crystal or amorphous.
6. The novel battery according to claim 1, wherein the solid interface protective layer is prepared on both surfaces of the solid electrolyte by means of slurry coating, or the solid electrolyte is immersed in the slurry of the solid interface protective layer, and then subjected to pulling and drying several times, thereby preparing the solid interface protective layer on both surfaces of the solid electrolyte.
7. The novel battery of claim 1, further comprising a positive electrode reservoir and a negative electrode reservoir;
the solid electrolyte with solid interface protective layers on the surfaces of two sides is arranged between the anode liquid storage cavity and the cathode liquid storage cavity and is hermetically connected with the anode liquid storage cavity and the cathode liquid storage cavity through the shell, the non-solid anode is in contact with the solid interface protective layer on one side of the solid electrolyte through the anode liquid storage cavity, and the non-solid cathode is in contact with the solid interface protective layer on the other side of the solid electrolyte through the cathode liquid storage cavity.
8. The novel battery of claim 7, wherein the positive electrode reservoir, the negative electrode reservoir and the housing are made of a transparent material.
9. The novel battery of claim 1, further comprising a sheet of metallic lithium disposed in the non-solid negative electrode.
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