CN114497711A - Composite solid electrolyte and preparation method thereof - Google Patents
Composite solid electrolyte and preparation method thereof Download PDFInfo
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- CN114497711A CN114497711A CN202210092513.4A CN202210092513A CN114497711A CN 114497711 A CN114497711 A CN 114497711A CN 202210092513 A CN202210092513 A CN 202210092513A CN 114497711 A CN114497711 A CN 114497711A
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 128
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 76
- 239000010416 ion conductor Substances 0.000 claims abstract description 66
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000011247 coating layer Substances 0.000 claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 38
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 claims description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052744 lithium Inorganic materials 0.000 abstract description 12
- 150000004679 hydroxides Chemical class 0.000 abstract description 10
- 238000009830 intercalation Methods 0.000 abstract description 7
- 230000002687 intercalation Effects 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 6
- 239000011241 protective layer Substances 0.000 abstract description 5
- 210000001787 dendrite Anatomy 0.000 abstract description 3
- 230000035515 penetration Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 40
- 238000010438 heat treatment Methods 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 14
- 238000000227 grinding Methods 0.000 description 14
- 239000011812 mixed powder Substances 0.000 description 14
- 239000011268 mixed slurry Substances 0.000 description 14
- 229910019142 PO4 Inorganic materials 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910000000 metal hydroxide Inorganic materials 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 229910017677 NH4H2 Inorganic materials 0.000 description 6
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000001132 ultrasonic dispersion Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 150000004692 metal hydroxides Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 241000270722 Crocodylidae Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- LNNWVNGFPYWNQE-GMIGKAJZSA-N desomorphine Chemical compound C1C2=CC=C(O)C3=C2[C@]24CCN(C)[C@H]1[C@@H]2CCC[C@@H]4O3 LNNWVNGFPYWNQE-GMIGKAJZSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910010951 LiH2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000011533 mixed conductor Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/052—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
- H01M10/42—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/002—Inorganic electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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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)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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- Conductive Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a composite solid electrolyte, which comprises fast ion conductor type solid electrolyte particles and a coating layer coated on the surface of the fast ion conductor type solid electrolyte particles, wherein the coating layer is formed by layered double hydroxides with nitrate radical intercalation. The invention also discloses a preparation method of the composite solid electrolyte. The invention uses the characteristic of strong accessibility of inorganic layered materials as a flexible structure protective layer which is uniformly coated on the surface of the fast ion conductor solid electrolyte, can effectively inhibit interface side reaction and improve the interface stability of the fast ion conductor solid electrolyte, and because the layered double hydroxide of nitrate radical intercalation has the characteristics of strong orientation, fast ion oriented conduction and low electronic conductivity, the inorganic layered material can be used as the protective layer to inhibit the penetration of lithium dendrites on the surface of the electrolyte and further improve the safety of the solid battery. The preparation method has mild conditions, simple operation and low cost, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a composite solid electrolyte and a preparation method thereof.
Background
Compared with organic electrolyte, the solid electrolyte has more excellent mechanical property, wider electrochemical window and higher working temperature, can effectively improve the battery capacity, expand the application range of electrode materials and improve the excellent safety performance of the battery. Therefore, the all-solid-state metal lithium battery is widely considered as a necessary route for the development of lithium batteries in the future based on advantages in safety performance and energy density.
The fast ionic conductor type inorganic solid electrolyte has higher ionic conductivity and more excellent mechanical property, and has great application prospect in the aspect of solid batteries. However, fast ion conductor solid-state electrolytes typically contain multivalent cations and are thermodynamically unstable to metallic lithium, allowing insertion of metallic lithium therein to form an ion-electron mixed conductor. The self-discharge behavior of the battery is accelerated because lithium ions and electrons can continuously permeate at an ion-electron mixed interface. In addition, the solid electrolyte itself has high electron conductivity, which also causes deposition of metallic lithium along grain boundaries of the solid electrolyte to cause loss of battery capacity. For the reasons, the lithium ion battery prepared based on the inorganic solid electrolyte has poor stability and is easy to lose efficacy. At present, although a certain progress is made in the aspect of improving the stability of the solid electrolyte, the coating methods such as magnetron sputtering coating or high-temperature vapor deposition are mainly adopted for two surfaces of a pressed and formed solid electrolyte sheet, so that the requirements on equipment are high, the production conditions are harsh, and the requirements of actual production and application can not be met far based on the existing solid energy storage system.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a composite solid electrolyte and a preparation method thereof.
The composite solid electrolyte provided by the invention comprises fast ion conductor type solid electrolyte particles and a coating layer coated on the surface of the fast ion conductor type solid electrolyte particles, wherein the coating layer is formed by layered double hydroxides with nitrate radical intercalation.
Preferably, the nitrate-intercalated layered double hydroxide is [ M ]1-yNy(OH)2][NO3]yWherein M is a divalent metal cation Mg2+、Zn2+、Ni2+、Mn2+、Co2+、Cu2+In (1)At least one, N is trivalent metal cation Al3+、Cr3+Y is more than or equal to 0.17 and less than or equal to 0.34.
Preferably, the nitrate-intercalated layered double hydroxide has a thickness of 1-2 nm.
Preferably, the particle size D50 of the fast ion conductor type solid electrolyte particle is 3 μm or less.
Preferably, the fast ion conductor-type solid electrolyte particles are Li1+aRaTi2-a(PO4)3The material, a is more than 0.01 and less than 2, wherein R is at least one of Al, Ga, Fe, In and Cr.
Among them, the fast ion conductor type solid electrolyte particles can be prepared by a conventional method, and the preparation method is not particularly limited in the present invention. For example, it can be prepared by a solid phase method, specifically Li1+aAlaTi2-a(PO4)3The method of the material is as follows: mixing a lithium source, a titanium source, an aluminum source and a phosphorus source in a ratio of Li: ti: al: the element molar ratio of P is (1+ a) a (2-a): 3, ball milling, calcining at the temperature of 700-1+ aAlaTi2-a(PO4)3(ii) a Preferably, the titanium source is at least one of titanium dioxide and titanium carbide; the aluminum source is aluminum oxide; the lithium source is at least one of lithium carbonate, lithium nitrate, lithium dihydrogen phosphate and lithium hydroxide, and the phosphorus source is at least one of ammonium dihydrogen phosphate, lithium dihydrogen phosphate and phosphoric acid.
Preferably, the ratio of the mass of the coating layer to the mass of the fast ion conductor type solid electrolyte particles is (0.005-0.05): 1.
the preparation method of the composite solid electrolyte comprises the following steps:
s1, adding an M source and an N source into a mixed solution of formamide, sodium nitrate and water according to a certain molar ratio under a protective atmosphere, and stirring to react under an alkaline condition to obtain a nitrate radical intercalated layered double hydroxide dispersion liquid;
and S2, mixing the fast ion conductor type solid electrolyte particles with the nitrate radical intercalated layered double hydroxide dispersion liquid, and stirring to react under a protective atmosphere to obtain the electrolyte.
In the preparation method, stacking in the formation process of the double metal hydroxide is inhibited by adopting the sodium nitrate aqueous solution of formamide, so that a lamellar structure which is easier to coat is obtained.
Preferably, in S1, (0.05-0.15) g of N source, formamide, sodium nitrate, water: (7-11) mL: (0.08-0.17) g: 30 mL; the M source is at least one of zinc nitrate hexahydrate, magnesium nitrate hexahydrate, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, copper nitrate trihydrate and manganese nitrate hexahydrate, and the N source is at least one of aluminum nitrate nonahydrate and chromium nitrate nonahydrate.
Preferably, the stirring reaction in S1 is carried out at 80-120 deg.C and pH of 9-11 for 30-60 min.
Preferably, in S2, the stirring reaction temperature is room temperature, and the reaction time is 24-72 h.
Preferably, the protective atmosphere is one of nitrogen and argon.
The application of the composite solid electrolyte in a lithium ion battery.
A lithium ion battery comprises the composite solid electrolyte.
The invention has the following beneficial effects:
in the composite solid electrolyte, an inorganic flaky protection layer formed by nitrate radical intercalated layered double hydroxides uniformly coats the surface of the fast ion conductor type solid electrolyte particles, wherein the layered double hydroxides have unique structural characteristics, and a main layer plate of the layered double hydroxides is formed by metal cations, so that the layered double hydroxides are beneficial to adsorbing ions and molecules in electrolyte and have better protection on the solid electrolyte particles. Negative ions intercalated between the laminates of the lithium ion battery are used as weak bound charges of a compensation interlayer region, so that the lithium ion battery has the characteristics of strong orientation, high ion orientation conduction speed and low electronic conductivity, can inhibit the penetration of lithium dendrites on the surface of an electrolyte as a protective layer, and further improves the safety of the solid battery. The nitrate radical intercalated layered double hydroxide is preferably adopted in the invention, and the preparation and stripping effectiveness is mainly considered, so that a flaky protective layer with stronger accessibility is obtained for more efficient stripping. The method can effectively inhibit penetration of the lithium dendrite, improve the interface stability of the solid electrolyte and further improve the stability of the lithium ion battery.
According to the invention, on one hand, the characteristic of strong accessibility of the flexible surface of the lamellar inorganic material is utilized, on the other hand, the lamellar stacking generated in the process of forming the double-metal hydroxide is inhibited by adopting the sodium nitrate aqueous solution of formamide, so that a lamellar structure which is easier to coat is obtained, and thus, the uniform coating of the surface of the fast ion conductor solid electrolyte is realized. Compared with the common coating method for performing magnetron sputtering coating or high-temperature vapor deposition on two sides of the pressed solid electrolyte sheet, the method can directly coat the solid electrolyte particles, has mild reaction conditions, is simple to operate, has high coating efficiency, good protection effect and strong universality, and is very suitable for large-scale industrial production.
Drawings
Fig. 1 is a photograph of example 4 and comparative example 1 for Li stability test, wherein the left side of fig. 1 is example 4 and the right side is comparative example 1.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
Preparing fast ion conductor type solid electrolyte particles:
2.42g of Li2CO3、0.71g Al2O3、6.2g TiO2And 16.1g NH4H2PO4Grinding in a mortar for 30min to obtain mixed powder; sequentially adding the mixed powder and zirconia balls into 40mL of ethanol, and performing ball milling in a planetary ball mill for 12 hours at the rotating speed of 300r/min to obtain mixed slurry; heating the mixed slurry in an oven at 80 ℃ until ethanol is completely volatilized, heating the obtained solid substance in a muffle furnace at the heating rate of 2 ℃/min to 1000 ℃, then carrying out heat preservation and calcination for 10h, and uniformly grinding to obtain the fast ion conductor type solid-state electricityThe electrolyte particles comprise Li-Al-Ti-phosphate1.3Al0.3Ti1.7(PO4)3。
Preparing a composite solid electrolyte:
s1, adding 0.08g of NaNO under the nitrogen protection atmosphere3Adding 30mL of water, stirring until the water is dissolved, adding 10mL of formamide, and stirring for 1h to obtain a mixed solution; to the mixed solution was added 0.13g of Mg (NO) in turn3)2·6H2O and 0.09g Al (NO)3)3·9H2O, stirring uniformly at 80 ℃, then slowly dropwise adding NaOH solution with the concentration of 0.25mol/L to adjust the pH value to 10, preserving the temperature, stirring and reacting for 30min to obtain nitrate radical intercalated layered double hydroxide dispersion liquid;
s2, adding 5g of LATP particles into the nitrate radical intercalated layered double hydroxide dispersion liquid prepared by the S1, performing ultrasonic dispersion for 10min, then stirring and reacting for 24h at room temperature, and washing the obtained solid substances with water and ethanol respectively after centrifugation to obtain the composite solid electrolyte.
The prepared composite solid electrolyte comprises fast ion conductor type solid electrolyte particles and a coating layer coated on the surface of the fast ion conductor type solid electrolyte particles, wherein the coating layer is formed by nitrate radical intercalated flaky double metal hydroxides; wherein the nitrate radical intercalated layered double hydroxide is [ Mg0.66Al0.34(OH)6][NO3]0.34The particle size D50 of the fast ion conductor type solid electrolyte particles was 2.13 μm, and the ratio of the mass of the coating layer to the mass of the fast ion conductor type solid electrolyte particles was 0.01: 1.
example 2
Preparing fast ion conductor type solid electrolyte particles:
8.57g of LiH2PO4、1.18g Al2O3、5.5g TiO2And 8.56g NH4H2PO4Grinding in a mortar for 30min to obtain mixed powder; sequentially adding the mixed powder and zirconia balls into 40mL of ethanol, and carrying out ball milling in a planetary ball mill for 12 hours at the rotating speed of 300r/min to obtain mixed slurry; heating the mixed slurry in an oven at 80 deg.CUntil the ethanol is completely volatilized, heating the obtained solid substance to 900 ℃ in a muffle furnace at the heating rate of 2 ℃/min, then carrying out heat preservation and calcination for 15h, and grinding uniformly to obtain fast ion conductor type solid electrolyte particles, wherein the component of the fast ion conductor type solid electrolyte particles is lithium aluminum titanium phosphate (Li)1.5Al0.5Ti1.5(PO4)3。
Preparing a composite solid electrolyte:
s1, adding 0.08g of NaNO under the nitrogen protection atmosphere3Adding 30mL of water, stirring until the water is dissolved, adding 10mL of formamide, and stirring for 1h to obtain a mixed solution; 0.14g of Zn (NO) was added to the mixed solution in order3)2·6H2O and 0.09g Al (NO)3)3·9H2O, stirring uniformly at 80 ℃, then slowly dropwise adding NaOH solution with the concentration of 0.25mol/L to adjust the pH value to 10, preserving the temperature, stirring and reacting for 30min to obtain nitrate radical intercalated layered double hydroxide dispersion liquid;
s2, adding 5g of LATP particles into the nitrate radical intercalated layered double hydroxide dispersion liquid prepared by the S1, performing ultrasonic dispersion for 10min, then stirring and reacting for 24h at room temperature, and washing the obtained solid substances with water and ethanol respectively after centrifugation to obtain the composite solid electrolyte.
The prepared composite solid electrolyte comprises fast ion conductor type solid electrolyte particles and a coating layer coated on the surface of the fast ion conductor type solid electrolyte particles, wherein the coating layer is formed by layered double hydroxides with nitrate radical intercalation; wherein the nitrate radical intercalated layered double hydroxide is [ Zn ]0.66Al0.34(OH)2][NO3]0.34The particle size D50 of the fast ion conductor type solid electrolyte particles was 1.88 μm, and the ratio of the mass of the coating layer to the mass of the fast ion conductor type solid electrolyte particles was 0.02: 1.
example 3
Preparing fast ion conductor type solid electrolyte particles:
2.42g of Li2CO3、0.71g Al2O3、4.7g TiC、3.4g H3PO4And 14.3g NH4H2PO4Grinding in a mortar for 30min,obtaining mixed powder; sequentially adding the mixed powder and zirconia balls into 40mL of ethanol, and carrying out ball milling in a planetary ball mill for 12 hours at the rotating speed of 300r/min to obtain mixed slurry; heating the mixed slurry in an oven at 80 ℃ until ethanol is completely volatilized, heating the obtained solid substance in a muffle furnace to 700 ℃ at the heating rate of 2 ℃/min, then carrying out heat preservation and calcination for 8h, and grinding uniformly to obtain fast ion conductor type solid electrolyte particles, wherein the components of the fast ion conductor type solid electrolyte particles are lithium aluminum titanium phosphate Li1.3Al0.3Ti1.7(PO4)3。
Preparing a composite solid electrolyte:
s1, adding 0.08g of NaNO under the nitrogen protection atmosphere3Adding 30mL of water, stirring until the water is dissolved, adding 10mL of formamide, and stirring for 1h to obtain a mixed solution; to the mixed solution was added 0.21g of Mg (NO) in turn3)2·6H2O and 0.09g Al (NO)3)3·9H2O, stirring uniformly at 80 ℃, then slowly dropwise adding NaOH solution with the concentration of 0.25mol/L to adjust the pH value to 10, preserving the temperature, stirring and reacting for 30min to obtain nitrate radical intercalated layered double hydroxide dispersion liquid;
s2, adding 5g of LATP particles into the nitrate radical intercalated layered double hydroxide dispersion liquid prepared by the S1, performing ultrasonic dispersion for 10min, then stirring and reacting for 24h at room temperature, and washing the obtained solid substances with water and ethanol respectively after centrifugation to obtain the composite solid electrolyte.
The prepared composite solid electrolyte comprises fast ion conductor type solid electrolyte particles and a coating layer coated on the surface of the fast ion conductor type solid electrolyte particles, wherein the coating layer is formed by layered double hydroxides with nitrate radical intercalation; wherein the nitrate radical intercalated layered double hydroxide is [ Mg0.75Al0.25(OH)2][NO3]0.25The particle size D50 of the fast ion conductor type solid electrolyte particles was 1.16 μm, and the ratio of the mass of the coating layer to the mass of the fast ion conductor type solid electrolyte particles was 0.04: 1.
example 4
Preparing fast ion conductor type solid electrolyte particles:
2.42g of Li2CO3、0.71g Al2O3、6.2g TiO2And 16.1g NH4H2PO4Grinding in a mortar for 30min to obtain mixed powder; sequentially adding the mixed powder and zirconia balls into 40mL of ethanol, and carrying out ball milling in a planetary ball mill for 12 hours at the rotating speed of 300r/min to obtain mixed slurry; heating the mixed slurry in an oven at 80 ℃ until ethanol is completely volatilized, heating the obtained solid substance to 900 ℃ at the heating rate of 2 ℃/min in a muffle furnace, then carrying out heat preservation and calcination for 10h, and grinding uniformly to obtain fast ion conductor type solid electrolyte particles, wherein the components of the fast ion conductor type solid electrolyte particles are lithium aluminum titanium phosphate Li1.3Al0.3Ti1.7(PO4)3。
Preparing a composite solid electrolyte:
s1, under the protection of argon, adding 0.08g of NaNO3Adding 30mL of water, stirring until the water is dissolved, adding 10mL of formamide, and stirring for 1h to obtain a mixed solution; 0.21g of Zn (NO) was added to the mixed solution in this order3)2·6H2O and 0.09g Al (NO)3)3·9H2O, stirring uniformly at 80 ℃, then slowly dropwise adding NaOH solution with the concentration of 0.25mol/L to adjust the pH value to 10, preserving the temperature, stirring and reacting for 30min to obtain nitrate radical intercalated layered double hydroxide dispersion liquid;
s2, adding 5g of LATP particles into the nitrate radical intercalated flaky double metal hydroxide dispersion liquid prepared by the S1, carrying out ultrasonic dispersion for 10min, then stirring and reacting for 24h at room temperature, and washing the obtained solid substances with water and ethanol respectively after centrifugation to obtain the composite solid electrolyte.
The prepared composite solid electrolyte comprises fast ion conductor type solid electrolyte particles and a coating layer coated on the surface of the fast ion conductor type solid electrolyte particles, wherein the coating layer is formed by layered double hydroxides with nitrate radical intercalation; wherein the nitrate radical intercalated layered double hydroxide is [ Zn ]0.75Al0.25(OH)2][NO3]0.25The particle size D50 of the fast ion conductor type solid electrolyte particles was 1.88 μm, the mass of the coating layer and the fast ion conductor type solid electrolyte particlesThe mass ratio of the particles is 0.02: 1.
example 5
Preparing fast ion conductor type solid electrolyte particles:
2.42g of Li2CO3、0.71g Al2O3、6.2g TiO2And 16.1g NH4H2PO4Grinding in a mortar for 30min to obtain mixed powder; sequentially adding the mixed powder and zirconia balls into 40mL of ethanol, and carrying out ball milling in a planetary ball mill for 12 hours at the rotating speed of 300r/min to obtain mixed slurry; heating the mixed slurry in an oven at 80 ℃ until ethanol is completely volatilized, heating the obtained solid substance to 800 ℃ at a heating rate of 2 ℃/min in a muffle furnace, then carrying out heat preservation and calcination for 5h, and uniformly grinding to obtain fast ion conductor type solid electrolyte particles, wherein the components of the fast ion conductor type solid electrolyte particles are lithium aluminum titanium phosphate Li1.3Al0.3Ti1.7(PO4)3。
Preparing a composite solid electrolyte:
s1, adding 0.08g of NaNO under the nitrogen protection atmosphere3Adding 30mL of water, stirring until the water is dissolved, adding 10mL of formamide, and stirring for 1h to obtain a mixed solution; 0.17g of Ni (NO) was added to the mixed solution in this order3)2·6H2O and 0.08g Cr (NO)3)3·9H2O, stirring uniformly at 80 ℃, then slowly dropwise adding NaOH solution with the concentration of 0.25mol/L to adjust the pH value to 10, preserving the temperature, stirring and reacting for 30min to obtain nitrate radical intercalated layered double hydroxide dispersion liquid;
s2, adding 5g of LATP particles into the nitrate radical intercalated layered double hydroxide dispersion liquid prepared by the S1, performing ultrasonic dispersion for 10min, then stirring and reacting for 24h at room temperature, and washing the obtained solid substances with water and ethanol respectively after centrifugation to obtain the composite solid electrolyte.
The prepared composite solid electrolyte comprises fast ion conductor type solid electrolyte particles and a coating layer coated on the surface of the fast ion conductor type solid electrolyte particles, wherein the coating layer is formed by nitrate radical intercalated double metal hydroxides; wherein the nitrate radical intercalated layered double hydroxide is [ Ni ]0.75Cr0.25(OH)2][NO3]0.25The particle size D50 of the fast ion conductor type solid electrolyte particles was 1.53 μm, and the ratio of the mass of the coating layer to the mass of the fast ion conductor type solid electrolyte particles was 0.02: 1.
example 6
Preparing fast ion conductor type solid electrolyte particles:
2.42g of Li2CO3、0.71g Al2O3、6.2g TiO2And 28g H3PO4Grinding in a mortar for 30min to obtain mixed powder; sequentially adding the mixed powder and zirconia balls into 40mL of ethanol, and carrying out ball milling in a planetary ball mill for 12 hours at the rotating speed of 300r/min to obtain mixed slurry; heating the mixed slurry in an oven at 80 ℃ until ethanol is completely volatilized, heating the obtained solid substance to 800 ℃ at a heating rate of 2 ℃/min in a muffle furnace, then carrying out heat preservation and calcination for 5h, and uniformly grinding to obtain fast ion conductor type solid electrolyte particles, wherein the components of the fast ion conductor type solid electrolyte particles are lithium aluminum titanium phosphate Li1.3Al0.3Ti1.7(PO4)3。
Preparing a composite solid electrolyte:
s1, adding 0.08g of NaNO under the nitrogen protection atmosphere3Adding 30mL of water, stirring until the water is dissolved, adding 10mL of formamide, and stirring for 1h to obtain a mixed solution; 0.17g of Cu (NO) was added to the mixed solution in this order3)2·3H2O，0.09g Al(NO3)3·9H2O, stirring uniformly at 80 ℃, then slowly dropwise adding NaOH solution with the concentration of 0.25mol/L to adjust the pH value to 10, preserving the temperature, stirring and reacting for 30min to obtain nitrate radical intercalated layered double hydroxide dispersion liquid;
s2, adding 5g of LATP particles into the nitrate radical intercalated layered double hydroxide dispersion liquid prepared by the S1, performing ultrasonic dispersion for 10min, then stirring and reacting for 24h at room temperature, and washing the obtained solid substances with water and ethanol respectively after centrifugation to obtain the composite solid electrolyte.
The prepared composite solid electrolyte comprises fast ion conductor type solid electrolyte particles and coating the fast ion conductor type solid electrolyte particlesThe coating layer on the surface is formed by layered double hydroxides with nitrate radical intercalation; wherein the nitrate radical intercalated flaky double metal hydroxide is [ Cu ]0.66Al0.34(OH)2][NO3]0.34The thickness of the film is 1-2 nm; the particle size D50 of the fast ion conductor type solid electrolyte particles was 1.78 μm, and the ratio of the mass of the coating layer to the mass of the fast ion conductor type solid electrolyte particles was 0.01: 1.
comparative example 1
Fast ion conductor type solid electrolyte particles were prepared (same method as in example 4):
2.42g of Li2CO3、0.71g Al2O3、6.2g TiO2And 16.1g NH4H2PO4Grinding in a mortar for 30min to obtain mixed powder; sequentially adding the mixed powder and zirconia balls into 40mL of ethanol, and carrying out ball milling in a planetary ball mill for 12 hours at the rotating speed of 300r/min to obtain mixed slurry; heating the mixed slurry in an oven at 80 ℃ until ethanol is completely volatilized, heating the obtained solid substance to 900 ℃ at the heating rate of 2 ℃/min in a muffle furnace, then carrying out heat preservation and calcination for 10h, and grinding uniformly to obtain fast ion conductor type solid electrolyte particles, wherein the components of the fast ion conductor type solid electrolyte particles are lithium aluminum titanium phosphate Li1.3Al0.3Ti1.7(PO4)3。
Test examples
The composite solid electrolytes prepared in examples 1 to 6 and the fast ion conductor type solid electrolyte particles prepared in comparative example 1 were respectively charged into a mold having a diameter of 13mm, pressed for 30 seconds using a pressure of 4Mpa, and pressed into a sheet to obtain a solid electrolyte sheet. Respectively dripping electrolyte [ LiPF ] on two sides of the obtained solid electrolyte sheet6-EC/DMC(EC:DMC＝1:1)]The Li battery is assembled by a positive electrode shell, a lithium sheet, a solid electrolyte sheet, a lithium sheet, foam nickel and a negative electrode shell in sequence, the battery is disassembled after being placed for 48 hours, and the surface of the solid electrolyte sheet is observed. The results show that the solid electrolyte sheets of examples 1-6 have only a small amount of black spots on the surface, indicating that the composite solid electrolyte containing the coating layer of the present invention has good interfacial stability, while the solid electrolyte sheet of comparative example 1 has a good surfaceA large number of black spots exist on the surface, which indicates that the uncoated fast ion conductor type solid electrolyte has poor interface stability. Referring to fig. 1, the solid electrolyte sheet of example 4 is shown on the left side of fig. 1, and the solid electrolyte sheet of comparative example 1 is shown on the right side of fig. 1, it can be seen that the solid electrolyte sheet of example 4 has only a small amount of black spots on the surface, and the solid electrolyte sheet of comparative example 1 has a large amount of black spots on the surface. The test results show that the interface stability of the composite solid electrolyte is obviously improved.
The ionic conductivity and impedance of the prepared solid electrolyte are tested, and the specific process is as follows: firstly, mounting a gold target on an ion sputtering instrument, placing a pressed solid electrolyte sample on a sample table, starting a power supply of the device, adjusting the current to 40mA, spraying gold on the surface of the sample for 4min, then opening an air inlet valve, taking out the sample piece after the air pressure is balanced, turning over the sample and placing the sample on the sample table, and repeating the steps to spray gold on the other surface. Then, respectively sticking steel sheets on the upper and lower bottom surfaces of the sample sheet after metal spraying, clamping the steel sheets by using a crocodile clamp, respectively connecting positive and negative electrode wires with two ends of the crocodile clamp, and carrying out alternating current impedance test, wherein the test frequency range is 106-0.01Hz and an amplitude of 10 mV. And finally, obtaining sample bulk impedance and grain boundary impedance data through circuit fitting, and according to a formula:
(where σ is ionic conductivity, L is sample piece thickness, D is sample piece bottom surface diameter, R1 is sample bulk impedance, and R2 is sample grain boundary impedance). The test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the coated samplesThe ionic conductivity of the product is not obviously different from that of an uncoated sample and can reach 10-4The magnitude of order shows that the nitrate radical intercalated double-metal hydroxide protective layer is coated on the surface of the sample, the ionic conductivity of the sample is not obviously influenced, and the coated sample can still exert high-efficiency Li+And (5) transmitting the effect.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A composite solid electrolyte comprising fast ion conductor type solid electrolyte particles and a coating layer formed on the surface of the fast ion conductor type solid electrolyte particles, wherein the coating layer is formed of a nitrate radical intercalated layered double hydroxide.
2. The composite solid electrolyte of claim 1, wherein the nitrate-intercalated layered double hydroxide is [ M ]1-yNy(OH)2][NO3]yWherein M is a divalent metal cation Mg2+、Zn2+、Ni2+、Mn2+、Co2+、Cu2+N is a trivalent metal cation Al3+、Cr3+Y is more than or equal to 0.17 and less than or equal to 0.34.
3. The composite solid electrolyte according to claim 1, wherein the nitrate-intercalated layered double hydroxide has a thickness of 1 to 2 nm.
4. The composite solid electrolyte of claim 1, wherein the fast ion conductor type solid electrolyte particles have a particle size D50 ≦ 3 μm.
5. According to claim 1The composite solid electrolyte is characterized in that the fast ion conductor type solid electrolyte particles are Li1+aRaTi2-a(PO4)3The material, a is more than 0.01 and less than 2, wherein R is at least one of Al, Ga, Fe, In and Cr.
6. The composite solid electrolyte of claim 1, wherein the ratio of the mass of the coating layer to the mass of the fast ion conductor type solid electrolyte particles is (0.005-0.05): 1.
7. a method of preparing a composite solid electrolyte according to any one of claims 1 to 6, comprising the steps of:
s1, adding an M source and an N source into a mixed solution of formamide, sodium nitrate and water according to a certain molar ratio under a protective atmosphere, and stirring to react under an alkaline condition to obtain a nitrate radical intercalated layered double hydroxide dispersion liquid;
and S2, mixing the fast ion conductor type solid electrolyte particles with the nitrate radical intercalated layered double hydroxide dispersion liquid, and stirring to react under a protective atmosphere to obtain the electrolyte.
8. The method for producing a composite solid electrolyte according to claim 7, wherein the ratio of the N source, formamide, sodium nitrate, and water in S1 is (0.05-0.15) g: (7-11) mL: (0.08-0.17) g: 30 mL; the M source is at least one of zinc nitrate hexahydrate, magnesium nitrate hexahydrate, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, copper nitrate trihydrate and manganese nitrate hexahydrate, and the N source is at least one of aluminum nitrate nonahydrate and chromium nitrate nonahydrate;
in S1, stirring and reacting at 80-120 deg.C and pH of 9-11 for 30-60 min;
in S2, the stirring reaction temperature is room temperature, and the reaction time is 24-72 h.
9. Use of a composite solid-state electrolyte according to any one of claims 1 to 6 in a lithium ion battery.
10. A lithium ion battery comprising the composite solid electrolyte of any one of claims 1 to 6.
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