CN115224368B - Solid electrolyte and lithium cathode integrated battery assembly, lithium solid battery and preparation method - Google Patents
Solid electrolyte and lithium cathode integrated battery assembly, lithium solid battery and preparation method Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 170
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 148
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007787 solid Substances 0.000 title claims description 24
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 119
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 118
- 239000011737 fluorine Substances 0.000 claims abstract description 118
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 12
- 238000007738 vacuum evaporation Methods 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 62
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 52
- 229910052717 sulfur Inorganic materials 0.000 claims description 52
- 239000011593 sulfur Substances 0.000 claims description 52
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 36
- 239000002002 slurry Substances 0.000 claims description 31
- 239000002033 PVDF binder Substances 0.000 claims description 29
- 238000011282 treatment Methods 0.000 claims description 29
- 239000011888 foil Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910052786 argon Inorganic materials 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- 238000007747 plating Methods 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 14
- 238000005498 polishing Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 7
- 239000006183 anode active material Substances 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000004917 carbon fiber Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims description 2
- 150000002221 fluorine Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 18
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 abstract description 14
- 238000005516 engineering process Methods 0.000 abstract description 12
- 210000001787 dendrite Anatomy 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000004927 fusion Effects 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 210000002381 plasma Anatomy 0.000 description 68
- 230000001105 regulatory effect Effects 0.000 description 37
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 26
- 229910001416 lithium ion Inorganic materials 0.000 description 26
- 238000012360 testing method Methods 0.000 description 24
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 23
- 230000014759 maintenance of location Effects 0.000 description 23
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 18
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 17
- 238000003682 fluorination reaction Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 125000004122 cyclic group Chemical group 0.000 description 11
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000001307 helium Substances 0.000 description 7
- 229910052734 helium Inorganic materials 0.000 description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 241001025261 Neoraja caerulea Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000000048 melt cooling Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000002203 sulfidic glass Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0423—Physical vapour deposition
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- 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
- H01M2004/027—Negative 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
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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
- H01M2300/0088—Composites
- H01M2300/0094—Composites in the form of layered products, e.g. coatings
-
- 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
Abstract
The invention discloses a battery component integrating a solid electrolyte and a lithium negative electrode and a preparation method thereof, wherein fluorine-containing gas is excited by a low-temperature plasma technology to generate high-activity fluorine-containing free radicals, so that a fluorine modified layer with strong lithium-philicity is formed on the surface of the solid electrolyte; fluorine can form lithium fluoride with lithium in situ in the electrochemical cycle process, so that the lithium is promoted to be deposited on the anode side in a homogenized manner, and simultaneously, the reduction of high-valence metal in the solid electrolyte by the lithium anode is effectively prevented; in order to further reduce interface resistance and accelerate the formation of in-situ lithium fluoride, the invention fuses or plates lithium on the surface of the fluorine modified layer of the solid electrolyte by methods such as vacuum evaporation, high-temperature fusion, magnetron sputtering and the like so as to strengthen interface contact. The battery component prepared by the invention can effectively reduce the internal resistance of the solid-state battery, optimize the interface current distribution, protect the solid-state electrolyte and lithium metal, inhibit the growth of lithium dendrite and finally improve the electrochemical performance of the lithium solid-state battery.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and relates to a battery assembly integrating a solid electrolyte and a lithium negative electrode and a preparation method thereof.
Background
In recent years, the rapid development of mobile electronic devices, electric vehicles, and power grid energy storage systems has greatly promoted the demand for lithium ion batteries having high energy density and high safety. At present, most of electrolyte used by the lithium ion battery is liquid organic electrolyte, but the characteristics of easy volatilization, flammability and explosiveness of the liquid organic electrolyte seriously affect the safety of the lithium ion battery in the use process. Meanwhile, the traditional polyolefin diaphragm is easy to be penetrated by lithium dendrites, so that internal short circuit of the battery is caused.
Compared with the traditional lithium ion battery using the diaphragm and the organic electrolyte, the solid-state lithium ion battery using the solid-state electrolyte has the advantages of strong designability, high theoretical capacity, high energy density, good safety performance and the like. The solid electrolyte can also be matched with a lithium negative electrode to construct a solid lithium metal battery with high energy density.
However, the practical use of solid electrolytes has also been hampered by the following:
1) The interface wettability is poor, and the interface resistance is too high when the interface wettability is contacted with lithium metal, so that the cycle performance of the solid-state battery is poor;
2) Part of the solid electrolyte is reduced by lithium metal to generate an interface insulating layer which does not conduct ions, and lithium metal is consumed and meanwhile transmission of lithium ions at an interface is blocked.
3) The solid electrolyte cannot completely inhibit the formation of lithium dendrites of the negative electrode, the lithium dendrites tend to grow along cracks and defects on the surface of the solid electrolyte, and under the condition of uneven current density, the lithium dendrites also penetrate through the solid electrolyte to cause internal short circuit of the battery, so that safety accidents are caused.
In order to inhibit dendrite growth, patent CN200810177712.5 reports a preparation method of a foam lithium negative electrode, mainly depositing lithium on the surface of a high-conductivity foam metal matrix, so as to prepare a foam lithium negative electrode with good cycle performance. But the introduction of a foam metal matrix reduces the energy density of the cell. Therefore, the use of lithium metal as a battery negative electrode to increase the energy density of the battery has been the focus of research on lithium solid-state batteries.
In order to improve the stability of the lithium anode, patent CN202010242419.3 forms a protective film on the surface of the metallic lithium sheet by vapor deposition technique. The method can effectively inhibit the growth of lithium dendrites and protect lithium metal. However, the lithium metal sheet prepared by this method is not amenable to such treatments as melt cooling, vacuum evaporation, magnetron sputtering, etc., and therefore has poor interfacial compatibility when in contact with solid electrolytes, and is not easily accessible for ideal interfacial contact.
In order to improve interface contact, patent CN201910751169.3 designs an integrated all-solid-state lithium-sulfur battery by hot-pressing the battery in the range of 50-100 ℃. The method can well improve the interface contact between the polymer electrolyte and the electrodes, but cannot improve the interface contact inside the inorganic ceramic solid electrolyte-based solid battery, and has certain limitation.
Disclosure of Invention
The invention aims to solve the problems that the prior art can not effectively reduce the interface resistance in a solid-state battery and can not fully improve the cycling stability of a lithium metal negative electrode, and provides a battery component with integrated solid electrolyte and lithium negative electrode and a preparation method thereof.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
in a first aspect, the present invention provides a method for preparing a solid electrolyte and lithium negative electrode integrated battery assembly, comprising the steps of:
step 1, placing a solid electrolyte in a plasma reactor, and vacuumizing;
step 2, introducing fluorine-containing gas into the plasma reactor;
step 3, adjusting the voltage and frequency of the plasma reactor to generate fluorine-containing plasma, so that the fluorine-containing plasma is loaded on the surface of the solid electrolyte, and the solid electrolyte with the modified fluorine surface is obtained;
And 4, plating lithium on the fluorine modified side of the fluorine surface modified solid electrolyte to obtain a battery component with the fluorine interface modified solid electrolyte and the lithium cathode integrated.
The method is further improved in that:
in the step 1, the solid electrolyte is an oxide solid electrolyte, a sulfide solid electrolyte, a polymer electrolyte or an organic/inorganic composite solid electrolyte; the plasma reactor adopts a dielectric barrier low-temperature plasma reactor; plasma deviceThe degree of vacuum after the sub-reactor was evacuated was 10 -3 ～10 -2 Pa。
In the step 2, the fluorine-containing gas comprises a mixture of inert gas and fluorine-containing gas;
the gas volume ratio is inert gas and fluorine-containing gas= (8:3) - (9.5:0.5);
the fluorine-containing gas comprises CF 4 、C 4 F 8 、C 5 F 8 、C 6 F 6 One or more than two kinds of mixed gas.
In the step 3, the voltage of the plasma reactor is 5-20 kV, the frequency is 30-70 kHz, the treatment time is 0.2-4 min, and the air flow speed is 0.5-5 slm; the fluorine surface modified solid electrolyte has a surface fluorine mass content of 5.02-74.60%.
In the step 4, the lithium plating adopts one or more of high-temperature lithium melting, magnetron sputtering lithium plating and vacuum evaporation lithium plating;
the high-temperature lithium melting is carried out in a glove box filled with inert gas: after combining the lithium sheet with the solid electrolyte, melting lithium at a high temperature of 200-350 ℃ and the thickness of the used lithium metal is 200-600 mu m;
The deposition amount of the vacuum evaporation lithium plating or the magnetron sputtering lithium plating is 5 gm to 100gm -2 。
And 5, carrying out the operations from the step 2 to the step 4 on the side which is not fluorinated and modified and is not plated with lithium again to prepare the battery component with the integrated solid electrolyte with the double-sided fluorine interface modification and the lithium cathode.
In a second aspect, the present invention provides a method for preparing a lithium solid-state battery, comprising the steps of:
step 1, polishing and grinding the side surface of the fluorine interface modified solid electrolyte and lithium negative electrode integrated battery assembly prepared by the method of any one of claims 1-5;
and 2, assembling the solid electrolyte and lithium cathode integrated battery assembly and a battery anode into a lithium solid battery, and pre-activating under low current density.
The method is further improved in that:
in the step 2, the positive electrode of the battery is a sulfur positive electrode sheet, a nickel cobalt lithium manganate positive electrode sheet, a lithium cobalt oxide positive electrode sheet or a lithium iron phosphate positive electrode sheet.
The preparation method of the sulfur positive plate comprises the following steps:
ball-milling and mixing a sulfur anode active material, conductive carbon black and a PVDF binder in an NMP solution through a ball mill to obtain sulfur active slurry; the mass ratio of the sulfur, the conductive carbon black and the PVDF binder is 70:20:10; uniformly coating sulfur active slurry on a carbon fiber current collector, and vacuum drying at 60-80 ℃ to obtain a sulfur positive plate with a sulfur load of 1-3 mgcm -2 ；
The preparation method of the nickel cobalt lithium manganate positive plate comprises the following steps:
adding a nickel cobalt lithium manganate active material, conductive carbon black and a PVDF binder into an NMP solution according to a mass ratio of 70:20:10, and magnetically stirring and uniformly mixing to obtain nickel cobalt lithium manganate active slurry; the nickel cobalt lithium manganate active slurry is uniformly coated on the aluminum foil, and is dried at the temperature of 60-80 ℃ to prepare the nickel cobalt lithium manganate positive plate with the loading capacity of 1-4 mgcm -2 。
In the step 2, the lithium solid-state battery is assembled in an argon glove box with oxygen content and water content lower than 0.1ppm, and the preactivation current density of the lithium solid-state battery is 0.05 ℃.
In a third aspect, the present invention provides a lithium solid-state battery prepared by the above method.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a layer of fluorine modified layer is deposited on the surface of the solid electrolyte by a low-temperature plasma technology, and lithium is plated on the fluorine modified surface by means of vacuum evaporation and the like. Compared with the technology, the low-temperature plasma technology has the advantages of low cost, little environmental hazard, high chemical reactivity of the generated free radicals and the like, and has wide application in the aspects of semiconductor industry, surface corrosion prevention, environmental protection, biomedicine and the like. However, the single plasma modification technology is difficult to solve the key problem of high interface resistance between the solid electrolyte and the lithium negative electrode, so that the application of the single plasma modification technology in the aspect of interface modification of the lithium solid-state battery has not been reported yet.
Drawings
For a clearer description of the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic diagram of a structure and a preparation flow of a battery assembly and a lithium solid-state battery of the invention in which a fluorine interface modified solid-state electrolyte and a lithium negative electrode are integrated.
Fig. 2 is an SEM image of the sulfur-coated carbon nanofiber anode in example 1 of the present invention.
Fig. 3 is a cycle chart of a lithium sulfur battery assembled from the fluorine interface modified LATP solid state electrolyte of example 1 of the present invention.
Fig. 4 is an ac impedance spectrum of a lithium sulfur battery assembled from a fluorine interface modified LATP solid state electrolyte of example 1 of the present invention.
Fig. 5 is a SEM and elemental distribution of the LAGP solid electrolyte of example 4 of the present invention.
FIG. 6 is an SEM image of a LAGP solid electrolyte modified by surface fluorine in example 4 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of the embodiments of the invention generally described and illustrated herein may be arranged and designed in a wide variety of different configurations.
Furthermore, the term "horizontal" if present does not mean that the component is required to be absolutely horizontal, but may be slightly inclined. As "horizontal" merely means that its direction is more horizontal than "vertical", and does not mean that the structure must be perfectly horizontal, but may be slightly inclined.
In the description of the embodiments of the present invention, it should also be noted that, unless explicitly specified and limited otherwise, the terms "disposed," "mounted," "connected," and "connected" should be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
The invention is described in further detail below with reference to examples:
referring to fig. 1, an embodiment of the invention discloses a preparation method of a battery assembly with a solid electrolyte and a lithium negative electrode integrated, which comprises the following steps:
and step 1, placing the solid electrolyte in a low-temperature plasma reactor, wherein an upper electrode of the reactor is connected with a high-voltage power supply, and the other electrode is grounded.
The solid electrolyte includes, but is not limited to, oxide type solid electrolyte, sulfide type solid electrolyte, polymer type electrolyte, organic/inorganic composite solid electrolyte. Plasma reactors include, but are not limited to, dielectric barrier low temperature plasma reactors.
And 2, vacuumizing the low-temperature plasma reactor in the step 1, and introducing fluorine-containing gas into the reactor. The fluorine-containing gas includes, but is not limited to, a mixture of inert gas such as helium, argon, nitrogen and the like and fluorine-containing gas, and the volume ratio of the inert gas to the fluorine-containing gas is (8:3) - (9.5:0.5), and the fluorine-containing gas includes, but is not limited to, CF 4 、C 4 F 8 、C 5 F 8 、C 6 F 6 One or more than two kinds of mixed gas. The vacuum degree of the vacuumized plasma processor is 10 -3 ～10 -2 Pa。
And 3, regulating the voltage and the frequency of the plasma reactor in the step 2 to generate a large amount of fluorine-containing plasmas, and finally loading the plasmas on the surface of the solid electrolyte to obtain the fluorine surface modified solid electrolyte. The voltage of the plasma reactor is 5-20 kV, the frequency is 30-70 kHz, the treatment time is 0.2-4 min, and the air flow speed is 0.5-5 slm. The fluorine mass content of the surface of the fluorine surface modified solid electrolyte sheet is 5.02-74.60%.
Step 4, the method comprises the following steps: 1. and (3) plating lithium on one side of the fluorine modified solid electrolyte sheet with the fluorine surface modified in the step (3) by using vacuum evaporation to obtain a battery component with the fluorine interface modified solid electrolyte and a lithium negative electrode integrated.
The lithium plating method includes, but is not limited to, one or more of high temperature melting, magnetron sputtering, vacuum evaporation and the like. Wherein, the method for melting lithium at high temperature is carried out in a glove box filled with inert gas: after the lithium sheet is combined with the solid electrolyte, lithium is melted under high temperature conditions, the melting temperature is 200-400 ℃, and the thickness of the used lithium metal is 200-600 mu m. The deposition amount of the vacuum evaporation lithium plating or the magnetron sputtering lithium plating is 5-100 g m -2 。
And 5, polishing and grinding the side surface of the battery assembly with the fluorine interface modified solid electrolyte and the lithium negative electrode in the step 4.
In another possible embodiment, the operations of steps 2 to 5 may be performed again on the non-fluorinated modified, non-lithium-plated side of the battery assembly to prepare a battery assembly with a double sided fluorine interface modified solid electrolyte integrated with a lithium negative electrode, for applications including, but not limited to, assembly and testing of lithium-lithium symmetric batteries assembled at 0.1mA cm -2 Is 0.1mAh cm -2 Is recyclable in the face volume of (2)>250h, and overvoltage<80mV。
Another embodiment of the present invention provides a method for preparing a lithium solid-state battery, comprising the steps of:
Step 1, assembling a battery component and a battery positive electrode into a lithium solid-state battery, and pre-activating at a low current density. The battery positive electrode material includes, but is not limited to, one of sulfur, nickel cobalt lithium manganate, lithium cobaltate and lithium iron phosphate. The cell assembly process was all performed in an argon glove box with oxygen content and water content below 0.1ppm, and the pre-activation current density of the assembled cell was 0.05C.
The preparation method of the sulfur positive plate comprises the following steps:
and ball-milling and mixing the anode active material, the conductive carbon black and the PVDF binder in NMP solution through a ball mill to obtain sulfur active slurry. The mass ratio of the sulfur, the conductive carbon black and the PVDF adhesive is 70:20:10. Uniformly coating the obtained slurry on a carbon fiber current collector, and vacuum drying at 60-80 ℃ to obtain a sulfur positive plate with a sulfur load of 1-3 mg cm -2 . Initial capacity of lithium sulfur battery>1000mAh g -1 Capacity retention after 100 cycles>80％。
Initial capacity of lithium sulfur battery>1000mAh g -1 Capacity retention after 100 cycles>80％，
The preparation method of the nickel cobalt lithium manganate (NCM 811) positive plate comprises the following steps:
adding NCM811, conductive carbon black and PVDF binder into NMP solution in a mass ratio of 70:20:10, magnetically stirring and uniformly mixing, uniformly coating the obtained slurry on an aluminum foil, and drying at 60-80 ℃ to obtain an NCM811 positive plate with a load of 1-4 mg cm -2 . Initial capacity of lithium ion battery with NCM811 as positive electrode>190mAh g -1 Capacity retention after 100 cycles>85％。
And 2, performing cyclic charge and discharge test on the solid-state battery prepared in the step 1 through a blue-ray test system.
The application range of the fluorine interface modified solid electrolyte and lithium negative electrode integrated battery component prepared by the invention comprises, but is not limited to, solid lithium metal batteries, solid lithium sulfur batteries, solid lithium ion batteries and other systems.
The principle of the invention is as follows:
firstly, exciting fluorine-containing gas by a low-temperature plasma technology to generate high-activity fluorine-containing free radicals, so that a fluorine modified layer with strong lithium-philic property is formed on the surface of a solid electrolyte; fluorine can form lithium fluoride with lithium in situ in the electrochemical cycle process, so that the lithium is promoted to be deposited on the anode side in a homogenized manner, and simultaneously, the reduction of high-valence metal in the solid electrolyte by the lithium anode is effectively prevented; in order to further reduce interface resistance and accelerate the formation of in-situ lithium fluoride, the invention fuses or plates lithium on the surface of the fluorine modified layer of the solid electrolyte by methods such as vacuum evaporation, high-temperature fusion, magnetron sputtering and the like so as to strengthen interface contact.
In conclusion, the invention fully utilizes the advantages of the low-temperature plasma technology, and effectively solves the key problems of poor interface compatibility between the solid electrolyte and the lithium negative electrode, poor cycling stability of the lithium negative electrode, low energy density of the negative electrode, small application range of the preparation technology and the like in the prior art. The battery component prepared by the method can effectively reduce the internal resistance of the solid-state battery, optimize the interface current distribution, protect the solid-state electrolyte and lithium metal, inhibit the growth of lithium dendrite and finally improve the electrochemical performance of the lithium solid-state battery.
The invention also has the following advantages:
(1) The inorganic ceramic solid electrolyte with high safety is selected, and the surface of the solid electrolyte is modified by using a low-temperature plasma modification technology.
The traditional chemical surface modification method is easy to introduce various substances such as water, organic solvents and the like, but LLZTO and other solid electrolytes are easy to react with water, so that the physical and chemical properties of the solid electrolytes are changed. The low-temperature plasma technology has the following characteristics in the treatment process:
only active free radicals are generally generated, other reactants are not required to be introduced, and the environmental hazard is small;
the uppermost atomic layer on the surface of the material is only modified generally, and the physical and chemical properties of the solid electrolyte are not changed;
can firmly load various high-activity chemical functional groups on the surface of the material, and improve the chemical reactivity of the surface of the material.
(2) And carrying out fluorination modification on the surface of the solid electrolyte.
Fluorine can improve the surface stability of the solid electrolyte and form an SEI layer containing LiF with lithium in situ during electrochemical cycling. LiF not only can optimize interfacial current distribution, promote the homogenized deposition of lithium on the negative electrode side, inhibit lithium dendriteLi formation, which also improves interface + The conductivity has remarkable improvement effect on the electrochemical performance of the solid-state battery.
Therefore, the invention selects fluorocarbon gas as fluorine modified gas, and carries out fluorination modification on the surface of the solid electrolyte by a low-temperature plasma technology. During the discharge process, the plasma discharge region forms various highly reactive species (Ar) + 、F、F - 、CF 3 + 、CF 2 2+ 、CF 3 - Etc.), the fluorine-containing species may be firmly supported on the surface of the solid electrolyte during this process, thereby obtaining a surface-fluorinated solid electrolyte.
(3) Lithium is melted or plated on the surface of the solid electrolyte modified by fluorination by a high-temperature melting cooling method, a vacuum evaporation method or a magnetron sputtering method, so that the combination of the solid electrolyte with the surface fluorinated and a lithium metal negative electrode is further enhanced, the interface resistance is reduced, and favorable conditions are provided for the formation of interface LiF in the electrochemical circulation process.
Example 1:
step 1, placing an oxide type LATP solid electrolyte (with the diameter of 15mm and the thickness of 0.8 mm) in a low-temperature plasma reactor, wherein an upper electrode of the reactor is connected with a high-voltage power supply, and the other electrode is grounded;
step 2, vacuumizing the low-temperature plasma reactor in the step 1 (the vacuum degree is less than or equal to 8 multiplied by 10) -3 Pa), introducing a mixed gas of helium and fluorocarbon gas with the volume ratio of 9.5:0.5 into the reaction cavity through the gas guide hole, wherein the fluorocarbon gas is C 6 F 6 ；
Step 3, regulating the voltage of the plasma reactor in the step 2 to 5kV, regulating the frequency to 30kHz, regulating the air flow speed to 1slm, and obtaining a LATP solid electrolyte sheet with a fluorine surface modified after the treatment time is 1min, wherein the surface fluorine content is 15.8%;
step 4, placing the LATP solid electrolyte sheet with the fluorine surface modified in the step 3 into a sample chamber of a vacuum evaporator, and placing a massive lithium source into the sample chamber, wherein the purity of the LATP solid electrolyte sheet is improved>99.9%, regulating the temperature to 500 ℃ and the vacuum degree less than or equal to 5 multiplied by 10 -3 Pa, an evaporation current of 40A, a treatment time of 6min, a lithium deposition amount of 20g m -2 Obtaining the embodimentA fluorine interface modified solid electrolyte and lithium negative electrode integrated battery assembly.
Step 5, polishing and grinding the side surface of the battery component integrated with the fluorine interface modified solid electrolyte and the lithium negative electrode in the step 4;
and 6, assembling the battery assembly and the sulfur anode in the step 5 into a solid-state lithium sulfur battery, wherein the assembling process is carried out in an argon glove box with oxygen content and water content lower than 0.1 ppm. Sulfur positive electrode preparation process: and ball-milling and mixing the anode active material, the conductive carbon black and the PVDF binder in NMP solution through a ball mill to obtain sulfur active slurry. The mass ratio of the sulfur, the conductive carbon black and the PVDF adhesive is 70:20:10. Uniformly coating the obtained slurry on a carbon fiber current collector, and vacuum drying at 60 ℃ to obtain a sulfur positive plate with a sulfur loading capacity of 1.5mg cm -2 Fig. 2 is an SEM image of the sulfur positive electrode. The prepared battery is circularly activated for 5 circles under the current density of 0.05C;
step 7, the solid-state lithium sulfur battery assembled in step 6 is subjected to cyclic charge and discharge test by a blue battery test system, the current density is 0.1C, and as shown in figure 3, the initial capacity of the battery is 1119mAh g -1 After 100 circles of circulation, the capacity is 896.0mAh g -1 The capacity retention rate was 80.0%, and fig. 4 shows an ac impedance spectrum of the battery.
Step 8, as a comparison, assembling the LATP solid electrolyte, the lithium foil and the sulfur positive plate which are not subjected to surface fluorination treatment into a solid lithium sulfur battery under the same conditions, wherein the initial capacity of the battery is 941.9mAh g at 0.1C multiplying power -1 The capacity is only 334.2mAh g after 100 circles of circulation -1 The capacity retention was only 35.5%.
Example 2:
step 1, the plasma reactor is vacuumized (the vacuum degree is less than or equal to 8 multiplied by 10) -3 Pa), placing sulfide type LGPS solid electrolyte (with the diameter of 15mm and the thickness of 0.8 mm) on a lower glass plate of a low-temperature plasma reactor, wherein an upper electrode of the reactor is connected with a high-voltage power supply, and the other electrode is grounded;
step 2, introducing a mixed gas with the volume ratio of helium to fluorocarbon gas of 9:1 into a plasma reaction cavity, wherein the fluorocarbon gas is CF 4 And C 4 F 8 The volume ratio of the mixed gas is 1:1.
Step 3, regulating the voltage of the plasma reactor in the step 2 to 10kV, regulating the frequency to 40kHz, regulating the air flow speed to 2slm, and obtaining the LGPS solid electrolyte sheet with the fluorine surface modified after the treatment time is 2min, wherein the surface fluorine content is 27.5%;
step 4, the fluorine surface modified LGPS solid electrolyte in the step 3 is treated
The sheet is put into a magnetron sputtering chamber, lithium is used as a target material, and the purity is high>99.9%, maintaining cooling temperature of-25deg.C, vacuum degree less than or equal to 5×10 -3 Pa, deposition amount of lithium of 40g m -2 The fluorine interface-modified solid electrolyte and lithium negative electrode integrated battery assembly of this example was obtained.
Step 5, polishing and grinding the side surface of the battery component integrated with the fluorine interface modified solid electrolyte and the lithium negative electrode in the step 4;
and 6, assembling the battery assembly in the step 5 and the NCM811 positive electrode into a solid-state lithium ion battery, wherein the assembling process is carried out in an argon glove box with oxygen content and water content lower than 0.1 ppm. NCM811, conductive carbon black and PVDF binder are mixed uniformly in NMP solution to obtain positive electrode active slurry. The mass ratio of NCM811, conductive carbon black to PVDF binder is 70:20:10. Uniformly coating the obtained slurry on an aluminum foil, and drying at 60 ℃ to obtain an NCM811 positive plate with a load of 1.3mg cm -2 . The prepared battery is circularly activated for 5 circles under the current density of 0.05C;
step 7, carrying out cyclic charge and discharge test on the solid-state lithium ion battery assembled in the step 6 through a blue battery test system, wherein the current density is 0.1C, and the initial capacity is 198mAh g under the 0.1C multiplying power -1 After 100 circles, the capacity is 179mAh g -1 The capacity retention rate reaches 90.4%.
Step 8, as a comparison, pressing and assembling the LGPS solid electrolyte, the lithium foil and the NCM811 positive plate which are not subjected to surface fluorination treatment in a glove box to obtain a solid lithium ion battery, wherein the initial capacity of the battery is 186mAh g at 0.1C multiplying power -1 The capacity is only 115mAh g after 100 circles of circulation -1 Capacity retention rate is only61.8%.
Example 3:
step 1, placing PEO-based polymer solid electrolyte (with the diameter of 13mm and the thickness of 0.9 mm) on a lower glass plate of a low-temperature plasma reactor, wherein an upper electrode of the reactor is connected with a high-voltage power supply, and the other electrode is grounded;
step 2, vacuumizing the low-temperature plasma reactor in the step 1 (the vacuum degree is less than or equal to 8 multiplied by 10) -3 Pa), introducing a mixed gas with the volume ratio of helium to fluorocarbon gas of 8:2 into the reaction cavity through the gas guide hole, wherein the fluorocarbon gas is C with the volume ratio of 2:2:1 4 F 8 、C 5 F 8 、C 6 F 6 A mixed gas;
step 3, regulating the voltage of the plasma reactor in the step 2 to 15kV, regulating the frequency to 50kHz, regulating the air flow speed to 3slm, and obtaining a PEO-based polymer solid electrolyte sheet with a fluorine surface modified after the treatment time is 3min, wherein the surface fluorine content is 42.4%;
Step 4, polishing the side surface of the PEO-based polymer solid electrolyte with the fluorine surface modified in the step 3;
and 5, assembling the PEO-based polymer solid electrolyte with the fluorine surface modified in the step 4, a sulfur positive plate and a lithium foil into a solid lithium sulfur battery, wherein the assembling process is carried out in an argon glove box with oxygen content and water content lower than 0.1 ppm. The preparation process of the sulfur positive electrode comprises the following steps: and ball-milling and mixing the anode active material, the conductive carbon black and the PVDF binder in NMP solution through a ball mill to obtain sulfur active slurry. The mass ratio of the sulfur, the conductive carbon black and the PVDF adhesive is 70:20:10. Uniformly coating the obtained slurry on a carbon fiber current collector, and vacuum drying at 70 ℃ to obtain a sulfur positive plate with a sulfur loading capacity of 2.6mg cm -2 . The prepared battery is circularly activated for 5 circles under the current density of 0.05C;
step 6, carrying out cyclic charge and discharge test on the solid-state lithium sulfur battery assembled in the step 6 through a blue battery test system, wherein the current density is 0.1C, and the initial capacity is 1078mAh g -1 After 100 circles of circulation, the capacity is 912mAh g -1 The capacity retention was 84.6%.
Step 7, comparing the non-passed surfaceThe PEO-based polymer solid electrolyte after fluorination treatment, the lithium foil and the sulfur positive plate are assembled into a solid lithium sulfur battery under the same conditions, and the initial capacity of the battery is 924mAh g under the 0.1C multiplying power -1 After 100 circles, the capacity is only 496mAh g -1 The capacity retention was only 53.7%.
Example 4:
step 1, placing oxide LAGP solid electrolyte (diameter 15mm, thickness 0.8 mm) (the solid electrolyte SEM image and each element distribution diagram shown in figure 5) on a lower glass plate of a low-temperature plasma reactor, wherein an upper electrode of the reactor is connected with a high-voltage power supply, and the other electrode is grounded;
step 2, vacuumizing the plasma reactor (the vacuum degree is less than or equal to 8 multiplied by 10) -3 Pa), introducing a mixed gas with the volume ratio of helium to fluorocarbon gas of 7:3 into a plasma reaction cavity, wherein the fluorocarbon gas is CF 4 。
Step 3, regulating the voltage of the plasma reactor in the step 2 to 20kV, regulating the frequency to 60kHz, regulating the air flow speed to 4slm, and obtaining a fluorine surface modified LAGP solid electrolyte sheet (shown in a fluorine modified LAGP solid electrolyte SEM (scanning electron microscope) picture in FIG. 6) after the treatment time is 4min, wherein the surface fluorine content is 51.8%;
and 4, melting lithium on the surface of the fluorine surface modified LAGP solid electrolyte sheet in the step 3 in a glove box with the oxygen content and the water content of less than 0.1ppm, wherein the melting temperature is 210 ℃, and the thickness of the used lithium metal is 400 mu m. And (3) after keeping the temperature at the highest temperature for 3 seconds, starting to cool, and cooling to normal temperature to obtain the fluorine interface modified solid electrolyte and lithium negative electrode integrated battery assembly.
Step 5, polishing the side surface of the battery assembly formed by integrating the LAGP solid electrolyte modified by the fluorine interface and the lithium cathode in the step 4;
and 6, assembling the battery assembly in the step 5 and the NCM811 positive electrode into a solid-state lithium ion battery, wherein the assembling process is carried out in an argon glove box with oxygen content and water content lower than 0.1 ppm. NCM811, conductive carbon black and PVDF binder are mixed uniformly in NMP solution to obtain positive electrode active slurry. The mass ratio of NCM811, conductive carbon black to PVDF binder is 70:20:10. Uniformly coating the obtained slurry on aluminumDrying the foil at 80 ℃ to obtain NCM811 positive plate with load of 2.5mg cm -2 . The prepared battery is circularly activated for 5 circles under the current density of 0.05C;
step 7, carrying out cyclic charge and discharge test on the solid-state lithium ion battery assembled in the step 6 through a blue battery test system, wherein the current density is 0.2C, and the initial capacity is 198mAh g under the 0.2C multiplying power -1 After 100 circles, the capacity is 179mAh g -1 The capacity retention rate reaches 90.4%.
Step 8, as a comparison, pressing and assembling the LAGP solid electrolyte which is not subjected to surface fluorination treatment, a lithium foil and an NCM811 positive plate in a glove box to obtain a solid lithium ion battery, wherein the initial capacity of the battery is 186mAh g at 0.2C multiplying power -1 The capacity is only 115mAh g after 100 circles of circulation -1 The capacity retention was only 61.8%.
Example 5:
step 1, placing PVDF-HFP/LAGP double-layer composite solid electrolyte (with the diameter of 15mm and the thickness of 0.8 mm) on a lower glass plate of a low-temperature plasma reactor, wherein one side of the electrolyte PVDF-HFP faces upwards, carrying out surface fluorine modification on the electrolyte PVDF-HFP, connecting an upper electrode of the reactor with a high-voltage power supply, and connecting the other electrode of the reactor with the ground;
step 2, vacuumizing the plasma reactor (the vacuum degree is less than or equal to 8 multiplied by 10) -3 Pa), introducing a mixed gas with the volume ratio of helium to fluorocarbon gas of 8:3 into a plasma reaction cavity, wherein the fluorocarbon gas is CF 4 。
Step 3, regulating the voltage of the plasma reactor in the step 2 to 15kV, regulating the frequency to 70kHz, regulating the air flow speed to 3slm, and obtaining a PVDF-HFP/LAGP composite solid electrolyte sheet with a fluorine surface modified after the treatment time is 5min, wherein the fluorine content of the surface is 54.7%;
step 4, polishing the side surface of the PVDF-HFP/LAGP composite solid electrolyte modified by the fluorine interface in the step 3;
and 5, assembling the battery assembly in the step 4, the NCM811 positive electrode and the lithium foil into a solid-state lithium ion battery, wherein the assembling process is carried out in an argon glove box with oxygen content and water content lower than 0.1 ppm. The preparation process of the NCM positive plate comprises the following steps: NCM811, conductive carbon black and And uniformly mixing the PVDF binder in the NMP solution to obtain the positive electrode active slurry. The mass ratio of NCM811, conductive carbon black to PVDF binder is 70:20:10. Uniformly coating the obtained slurry on an aluminum foil, and drying at 70 ℃ to obtain an NCM811 positive plate with a load of 3.6mg cm -2 The prepared battery is circularly activated for 5 circles under the current density of 0.05C;
step 6, carrying out cyclic charge and discharge test on the solid-state lithium ion battery assembled in the step 5 through a blue battery test system, wherein the current density is 0.2C, and the initial capacity is 194mAh g under the 0.2C multiplying power -1 The capacity of the material after 100 circles is 180mAh g -1 The capacity retention rate reaches 92.8%.
Step 7, as a comparison, pressing and assembling PVDF-HFP/LAGP composite solid electrolyte which is not subjected to surface fluorination treatment, a lithium foil and an NCM811 positive plate in a glove box to obtain a solid lithium ion battery, wherein the initial capacity of the battery is 178mAh g at 0.2C multiplying power -1 The capacity is only 115mAh g after 100 circles of circulation -1 The capacity retention was only 64.6%.
Example 6:
step 1, placing oxide LAGP solid electrolyte (with the diameter of 15mm and the thickness of 0.8 mm) on a lower glass plate of a low-temperature plasma reactor, wherein an upper electrode of the reactor is connected with a high-voltage power supply, and the other electrode is grounded;
Step 2, vacuumizing the plasma reactor (the vacuum degree is less than or equal to 8 multiplied by 10) -3 Pa), introducing a mixed gas with the volume ratio of helium to fluorocarbon gas of 7:3 into a plasma reaction cavity, wherein the fluorocarbon gas is CF 4 。
Step 3, regulating the voltage of the plasma reactor in the step 2 to 20kV, regulating the frequency to 60kHz, regulating the air flow speed to 4slm, and obtaining a fluorine surface modified LAGP solid electrolyte sheet after the treatment time is 4min, wherein the surface fluorine content is 47.3%;
step 4, placing the LAGP solid electrolyte sheet with the fluorine surface modified in the step 3 into a magnetron sputtering chamber, and taking lithium as a target material to obtain the purity>99.9%, maintaining cooling temperature of-25deg.C, vacuum degree less than or equal to 5×10 -3 Pa, deposition amount of lithium of 40g m -2 Obtaining the fluorine interface modified solid electrolyte and lithium of the embodimentAnd a negative electrode integrated battery assembly.
Step 5, repeating the steps 1 to 4 on the non-fluorinated modified and non-lithium-plated side of the battery component in the step 4 to obtain a battery component with integrated double-sided fluorine interface modified solid electrolyte and lithium negative electrode;
step 6, polishing the side surface of the battery component with the double-sided fluorine interface modified solid electrolyte and the lithium negative electrode integrated in the step 5, and assembling the battery component into a lithium-lithium symmetrical battery;
step 7, the battery assembly in step 6 is tested at 0.1mA cm by a blue electric testing system -2 Is 0.1mAh cm -2 Lithium plating and stripping experiments were performed at a surface capacity of (2) and after 250h of cycling, the overvoltage was 58mV.
In contrast, the original LAGP solid electrolyte was assembled into a lithium-lithium symmetric battery under the same conditions and was measured at 0.1mA cm -2 Is 0.1mAh cm -2 Lithium plating and stripping experiments were performed at the surface capacity of (3), after 50 hours, the overvoltage was measured>700mV。
Example 7:
step 1, placing oxide LAGP solid electrolyte (with the diameter of 15mm and the thickness of 0.8 mm) on a lower glass plate of a low-temperature plasma reactor, wherein an upper electrode of the reactor is connected with a high-voltage power supply, and the other electrode is grounded;
step 2, vacuumizing the plasma reactor (the vacuum degree is less than or equal to 10) -2 Pa), introducing a mixed gas of nitrogen and fluorocarbon gas with the volume ratio of 9.5:0.5 into a plasma reaction cavity, wherein the fluorocarbon gas is C 6 F 6 。
Step 3, regulating the voltage of the plasma reactor in the step 2 to 15kV, regulating the frequency to 30kHz, regulating the air flow speed to 0.5slm, and obtaining a fluorine surface modified LAGP solid electrolyte sheet after the treatment time is 0.2min, wherein the surface fluorine content is 5.02%;
and 4, melting lithium on the surface of the fluorine surface modified LAGP solid electrolyte sheet in the step 3 in a glove box with the oxygen content and the water content of less than 0.1ppm, wherein the melting temperature is 200 ℃, and the thickness of the used lithium metal is 200 mu m. And (3) after keeping the temperature at the highest temperature for 3 seconds, starting to cool, and cooling to normal temperature to obtain the fluorine interface modified solid electrolyte and lithium negative electrode integrated battery assembly.
Step 5, polishing the side surface of the battery assembly formed by integrating the LAGP solid electrolyte modified by the fluorine interface and the lithium cathode in the step 4;
and 6, assembling the battery assembly in the step 5 and the NCM811 positive electrode into a solid-state lithium ion battery, wherein the assembling process is carried out in an argon glove box with oxygen content and water content lower than 0.1 ppm. NCM811, conductive carbon black and PVDF binder are mixed uniformly in NMP solution to obtain positive electrode active slurry. The mass ratio of NCM811, conductive carbon black to PVDF binder is 70:20:10. Uniformly coating the obtained slurry on an aluminum foil, and drying at 80 ℃ to obtain an NCM811 positive plate with a load of 2.5mg cm -2 . The prepared battery is circularly activated for 5 circles under the current density of 0.05C;
step 7, carrying out cyclic charge and discharge test on the solid-state lithium ion battery assembled in the step 6 through a blue battery test system, wherein the current density is 0.2C, and the initial capacity is 185mAh g under the 0.2C multiplying power -1 The capacity of the material after 100 circles is 168mAh g -1 The capacity retention rate reached 91.9%.
Step 8, as a comparison, pressing and assembling the LAGP solid electrolyte which is not subjected to surface fluorination treatment, a lithium foil and an NCM811 positive plate in a glove box to obtain a solid lithium ion battery, wherein the initial capacity of the battery is 180mAh g at 0.2C multiplying power -1 The capacity is only 113mAh g after 100 circles of circulation -1 The capacity retention was only 62.8%.
Example 8:
step 1, placing oxide LAGP solid electrolyte (with the diameter of 15mm and the thickness of 0.8 mm) on a lower glass plate of a low-temperature plasma reactor, wherein an upper electrode of the reactor is connected with a high-voltage power supply, and the other electrode is grounded;
step 2, vacuumizing the plasma reactor (the vacuum degree is less than or equal to 10) -3 Pa), introducing a mixed gas with the volume ratio of argon to fluorocarbon gas of 8:3 into a plasma reaction cavity, wherein the fluorocarbon gas is C 4 F 8 。
Step 3, regulating the voltage of the plasma reactor in the step 2 to 20kV, regulating the frequency to 50kHz, regulating the air flow speed to 5slm, and obtaining a fluorine surface modified LAGP solid electrolyte sheet after the treatment time is 4min, wherein the surface fluorine content is 74.60%;
and 4, melting lithium on the surface of the fluorine surface modified LAGP solid electrolyte sheet in the step 3 in a glove box with the oxygen content and the water content of less than 0.1ppm, wherein the melting temperature is 350 ℃, and the thickness of the used lithium metal is 600 mu m. And (3) after keeping the temperature at the highest temperature for 3 seconds, starting to cool, and cooling to normal temperature to obtain the fluorine interface modified solid electrolyte and lithium negative electrode integrated battery assembly.
Step 5, polishing the side surface of the battery assembly formed by integrating the LAGP solid electrolyte modified by the fluorine interface and the lithium cathode in the step 4;
And 6, assembling the battery assembly in the step 5 and the NCM811 positive electrode into a solid-state lithium ion battery, wherein the assembling process is carried out in an argon glove box with oxygen content and water content lower than 0.1 ppm. NCM811, conductive carbon black and PVDF binder are mixed uniformly in NMP solution to obtain positive electrode active slurry. The mass ratio of NCM811, conductive carbon black to PVDF binder is 70:20:10. Uniformly coating the obtained slurry on an aluminum foil, and drying at 80 ℃ to obtain an NCM811 positive plate with a load of 2.5mg cm -2 . The prepared battery is circularly activated for 5 circles under the current density of 0.05C;
step 7, carrying out cyclic charge and discharge test on the solid-state lithium ion battery assembled in the step 6 through a blue battery test system, wherein the current density is 0.2C, and the initial capacity is 1193mAh g under the 0.2C multiplying power -1 The capacity of the material after 100 circles is 176mAh g -1 The capacity retention rate reached 91.2%.
Step 8, as a comparison, pressing and assembling the LAGP solid electrolyte which is not subjected to surface fluorination treatment, a lithium foil and an NCM811 positive plate in a glove box to obtain a solid lithium ion battery, wherein the initial capacity of the battery is 179mAh g at 0.2C multiplying power -1 The capacity is only 125mAh g after 100 circles of circulation -1 The capacity retention was only 69.8%.
Example 9:
step 1, placing oxide LAGP solid electrolyte (with the diameter of 15mm and the thickness of 0.8 mm) on a lower glass plate of a low-temperature plasma reactor, wherein an upper electrode of the reactor is connected with a high-voltage power supply, and the other electrode is grounded;
step 2, vacuumizing the plasma reactor (the vacuum degree is less than or equal to 6 multiplied by 10) -3 Pa), introducing a mixed gas with the volume ratio of argon to fluorocarbon gas of 9:1 into a plasma reaction cavity, wherein the fluorocarbon gas is CF 4 。
Step 3, regulating the voltage of the plasma reactor in the step 2 to 12kV, regulating the frequency to 45kHz, regulating the air flow speed to 3slm, and obtaining a fluorine surface modified LAGP solid electrolyte sheet after the treatment time is 3min, wherein the surface fluorine content is 47.58%;
and 4, melting lithium on the surface of the fluorine surface modified LAGP solid electrolyte sheet in the step 3 in a glove box with the oxygen content and the water content of less than 0.1ppm, wherein the melting temperature is 240 ℃, and the thickness of the used lithium metal is 400 mu m. And (3) after keeping the temperature at the highest temperature for 3 seconds, starting to cool, and cooling to normal temperature to obtain the fluorine interface modified solid electrolyte and lithium negative electrode integrated battery assembly.
Step 5, polishing the side surface of the battery assembly formed by integrating the LAGP solid electrolyte modified by the fluorine interface and the lithium cathode in the step 4;
And 6, assembling the battery assembly in the step 5 and the NCM811 positive electrode into a solid-state lithium ion battery, wherein the assembling process is carried out in an argon glove box with oxygen content and water content lower than 0.1 ppm. NCM811, conductive carbon black and PVDF binder are mixed uniformly in NMP solution to obtain positive electrode active slurry. The mass ratio of NCM811, conductive carbon black to PVDF binder is 70:20:10. Uniformly coating the obtained slurry on an aluminum foil, and drying at 80 ℃ to obtain an NCM811 positive plate with a load of 2.5mg cm -2 . The prepared battery is circularly activated for 5 circles under the current density of 0.05C;
step 7, carrying out cyclic charge and discharge test on the solid-state lithium ion battery assembled in the step 6 through a blue battery test system, wherein the current density is 0.2C, and the initial capacity is 199mAh g under the 0.2C multiplying power -1 After 100 circles of circulation, the capacity is 183mAh g -1 The capacity retention rate reached 92.0%.
Step 8, comparing the LAGP solid electrolyte without surface fluorination treatment with lithium foilPressing and assembling an NCM811 positive plate into a solid lithium ion battery in a glove box, wherein the initial capacity of the battery is 182mAh g under the 0.2C multiplying power -1 The capacity is only 111mAh g after 100 circles of circulation -1 The capacity retention was only 61.0%.
Example 10:
step 1, placing an oxide type LATP solid electrolyte (with the diameter of 15mm and the thickness of 0.8 mm) in a low-temperature plasma reactor, wherein an upper electrode of the reactor is connected with a high-voltage power supply, and the other electrode is grounded;
step 2, vacuumizing the low-temperature plasma reactor in the step 1 (the vacuum degree is less than or equal to 4 multiplied by 10) -3 Pa), introducing a mixed gas of argon and fluorocarbon gas with the volume ratio of 9:1 into the reaction cavity through the gas guide hole, wherein the fluorocarbon gas is CF 4 ；
Step 3, regulating the voltage of the plasma reactor in the step 2 to 15kV, regulating the frequency to 45kHz, regulating the air flow speed to 3slm, and obtaining a LATP solid electrolyte sheet with a fluorine surface modified after 2.5min of treatment time, wherein the surface fluorine content is 50.24%;
step 4, placing the LATP solid electrolyte sheet with the fluorine surface modified in the step 3 into a sample chamber of a vacuum evaporator, and placing a massive lithium source into the sample chamber, wherein the purity of the LATP solid electrolyte sheet is improved>99.9%, regulating the temperature to 500 ℃ and the vacuum degree less than or equal to 5 multiplied by 10 -3 Pa, an evaporation current of 40A, a treatment time of 6min, a lithium deposition amount of 5g m -2 The fluorine interface-modified solid electrolyte and lithium negative electrode integrated battery assembly of this example was obtained.
Step 5, polishing and grinding the side surface of the battery component integrated with the fluorine interface modified solid electrolyte and the lithium negative electrode in the step 4;
And 6, assembling the battery assembly and the sulfur anode in the step 5 into a solid-state lithium sulfur battery, wherein the assembling process is carried out in an argon glove box with oxygen content and water content lower than 0.1 ppm. Sulfur positive electrode preparation process: and ball-milling and mixing the anode active material, the conductive carbon black and the PVDF binder in NMP solution through a ball mill to obtain sulfur active slurry. The mass ratio of the sulfur, the conductive carbon black and the PVDF adhesive is 70:20:10. Uniformly coating the obtained slurry on a carbon fiber current collector, and vacuum drying at 60 ℃ to obtain a sulfur positive plate and sulfur loadThe amount was 1.5mg cm -2 . The prepared battery is circularly activated for 5 circles under the current density of 0.05C;
step 7, carrying out cyclic charge and discharge test on the solid-state lithium sulfur battery assembled in the step 6 through a blue battery test system, wherein the current density is 0.1C, and the initial capacity is 1104mAh g -1 After 100 circles, the capacity is 902mAh g -1 The capacity retention was 81.7%.
Step 8, as a comparison, assembling the LATP solid electrolyte, the lithium foil and the sulfur positive plate which are not subjected to surface fluorination treatment into a solid lithium sulfur battery under the same conditions, wherein the initial capacity of the battery is 1034mAh g at 0.1C multiplying power -1 The capacity after 100 circles is only 588mAh g -1 The capacity retention was only 56.9%.
Example 11:
step 1, placing an oxide type LATP solid electrolyte (with the diameter of 15mm and the thickness of 0.8 mm) in a low-temperature plasma reactor, wherein an upper electrode of the reactor is connected with a high-voltage power supply, and the other electrode is grounded;
step 2, vacuumizing the low-temperature plasma reactor in the step 1 (the vacuum degree is less than or equal to 4 multiplied by 10) -3 Pa), introducing a mixed gas of argon and fluorocarbon gas with the volume ratio of 9:1 into the reaction cavity through the gas guide hole, wherein the fluorocarbon gas is CF 4 ；
Step 3, regulating the voltage of the plasma reactor in the step 2 to 15kV, regulating the frequency to 45kHz, regulating the air flow speed to 3slm, and obtaining a LATP solid electrolyte sheet with a fluorine surface modified after 2.5min of treatment time, wherein the surface fluorine content is 49.75%;
step 4, placing the LATP solid electrolyte sheet with the fluorine surface modified in the step 3 into a sample chamber of a vacuum evaporator, and placing a massive lithium source into the sample chamber, wherein the purity of the LATP solid electrolyte sheet is improved>99.9%, regulating the temperature to 500 ℃ and the vacuum degree less than or equal to 5 multiplied by 10 -3 Pa, an evaporation current of 40A, a treatment time of 6min, and a lithium deposition amount of 100g m -2 The fluorine interface-modified solid electrolyte and lithium negative electrode integrated battery assembly of this example was obtained.
Step 5, polishing and grinding the side surface of the battery component integrated with the fluorine interface modified solid electrolyte and the lithium negative electrode in the step 4;
And 6, assembling the battery assembly and the sulfur anode in the step 5 into a solid-state lithium sulfur battery, wherein the assembling process is carried out in an argon glove box with oxygen content and water content lower than 0.1 ppm. Sulfur positive electrode preparation process: and ball-milling and mixing the anode active material, the conductive carbon black and the PVDF binder in NMP solution through a ball mill to obtain sulfur active slurry. The mass ratio of the sulfur, the conductive carbon black and the PVDF adhesive is 70:20:10. Uniformly coating the obtained slurry on a carbon fiber current collector, and vacuum drying at 60 ℃ to obtain a sulfur positive plate with a sulfur loading capacity of 1.5mg cm -2 . The prepared battery is circularly activated for 5 circles under the current density of 0.05C;
step 7, carrying out cyclic charge and discharge test on the solid-state lithium sulfur battery assembled in the step 6 through a blue battery test system, wherein the current density is 0.1C, and the initial capacity is 1098mAh g -1 After 100 circles, the capacity is 898mAh g -1 The capacity retention was 81.8%.
Step 8, as a comparison, assembling the LATP solid electrolyte which is not subjected to surface fluorination treatment, a lithium foil and a sulfur positive plate into a solid lithium sulfur battery under the same conditions, wherein the initial capacity of the battery is 985mAh g at 0.1C multiplying power -1 The capacity after 100 circles of circulation is only 553mAh g -1 The capacity retention was only 56.1%.
The result shows that the fluorine interface modified solid electrolyte and lithium negative electrode integrated composite material prepared by the invention can obviously improve the electrochemical performance of a solid lithium battery, thereby having good development prospect.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. A method of preparing a lithium solid-state battery, comprising the steps of:
step 1, placing a solid electrolyte in a plasma reactor, and vacuumizing; solid stateThe electrolyte is oxide type solid electrolyte, sulfide type solid electrolyte, polymer type electrolyte or organic/inorganic composite solid electrolyte; the plasma reactor adopts a dielectric barrier low-temperature plasma reactor; the vacuum degree of the plasma reactor after vacuumizing is 10 -3 ~10 - 2 Pa；
Step 2, introducing fluorine-containing gas into the plasma reactor; the fluorine-containing gas includes a mixture of an inert gas and a fluorine-containing gas; the gas volume ratio is inert gas and fluorine-containing gas= (8:3) - (9.5:0.5); the fluorine-containing gas comprises CF 4 、C 4 F 8 、C 5 F 8 、C 6 F 6 One or more than two kinds of mixed gas;
step 3, adjusting the voltage and frequency of the plasma reactor to generate fluorine-containing plasma, so that the fluorine-containing plasma is loaded on the surface of the solid electrolyte, and the solid electrolyte with the modified fluorine surface is obtained; the voltage of the plasma reactor is 5-20 kV, the frequency is 30-70 kHz, the treatment time is 0.2-4 min, and the air flow speed is 0.5-5 slm; the mass content of fluorine on the surface of the fluorine surface modified solid electrolyte is 5.02% -74.60%;
step 4, plating lithium on the fluorine modified side of the fluorine surface modified solid electrolyte to obtain a battery component with a fluorine interface modified solid electrolyte and a lithium cathode integrated; the lithium plating adopts one or more of high-temperature lithium melting, magnetron sputtering lithium plating and vacuum evaporation lithium plating; the high-temperature lithium melting is carried out in a glove box filled with inert gas: after combining the lithium sheet with the solid electrolyte, melting lithium at a high temperature of 200-350 ℃ and using a lithium metal thickness of 200-600 mu m; the deposition amount of lithium in the vacuum evaporation lithium plating or the magnetron sputtering lithium plating is 5-100 g m -2 ；
Step 5, carrying out the operations from step 2 to step 4 on the side which is not fluorinated and modified and is not plated with lithium again to prepare the battery component with the integrated solid electrolyte modified by the double-sided fluorine interface and the lithium cathode;
Step 6, polishing and grinding the side surface of the prepared fluorine interface modified solid electrolyte and lithium negative electrode integrated battery assembly;
and 7, assembling the solid electrolyte and lithium cathode integrated battery assembly and a battery anode into a lithium solid battery, and pre-activating under low current density.
2. The method for preparing a lithium solid-state battery according to claim 1, wherein in the step 2, the battery positive electrode is a sulfur positive electrode sheet, a nickel cobalt lithium manganate positive electrode sheet, a lithium cobaltate positive electrode sheet or a lithium iron phosphate positive electrode sheet; the lithium solid-state battery was assembled in an argon glove box having an oxygen content and a water content of less than 0.1 ppm, and the pre-activation current density of the lithium solid-state battery was 0.05C.
3. The method for producing a lithium solid-state battery according to claim 2, wherein the method for producing a sulfur positive electrode sheet is as follows:
ball-milling and mixing a sulfur anode active material, conductive carbon black and a PVDF binder in an NMP solution through a ball mill to obtain sulfur active slurry; the mass ratio of the sulfur, the conductive carbon black and the PVDF binder is 70:20:10; uniformly coating sulfur active slurry on a carbon fiber current collector, and vacuum drying at 60-80 ℃ to obtain a sulfur positive plate with a sulfur load of 1-3 mg cm -2 ；
The preparation method of the nickel cobalt lithium manganate positive plate comprises the following steps:
adding a nickel cobalt lithium manganate active material, conductive carbon black and a PVDF binder into an NMP solution according to a mass ratio of 70:20:10, and magnetically stirring and uniformly mixing to obtain nickel cobalt lithium manganate active slurry; uniformly coating nickel cobalt lithium manganate active slurry on an aluminum foil, and drying at 60-80 ℃ to obtain a nickel cobalt lithium manganate positive plate with a load capacity of 1-4 mg cm -2 。
4. A lithium solid-state battery prepared by the method of any one of claims 1-3.
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