CN115954530A - Solid electrolyte, solid electrolyte membrane, and all-solid-state lithium battery - Google Patents
Solid electrolyte, solid electrolyte membrane, and all-solid-state lithium battery Download PDFInfo
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 72
- 239000012528 membrane Substances 0.000 title claims abstract description 40
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000002071 nanotube Substances 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 40
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 18
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- -1 polyethylene Polymers 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 4
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 4
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 4
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 4
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000767 polyaniline Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910013372 LiC 4 Inorganic materials 0.000 claims description 3
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 3
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 claims description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- HAUKUGBTJXWQMF-UHFFFAOYSA-N lithium;propan-2-olate Chemical compound [Li+].CC(C)[O-] HAUKUGBTJXWQMF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920006254 polymer film Polymers 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002121 nanofiber Substances 0.000 description 8
- 238000000807 solvent casting Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 4
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052621 halloysite Inorganic materials 0.000 description 3
- 229910003480 inorganic solid Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a solid electrolyte, a solid electrolyte membrane and an all-solid-state lithium battery, wherein the solid electrolyte comprises the following components in percentage by mass: the invention obtains a solid electrolyte by blending the nanotube material, the lithium salt and the polymer, the solid electrolyte has high ionic conductivity, wider electrochemical window, good thermal stability and processability, and is easy to prepare into a polymer film, the solid electrolyte film prepared by the solid electrolyte has good performance, and an all-solid-state lithium battery assembled by the electrolyte can work in a wider temperature range and has good multiplying power and cycle performance.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a solid electrolyte, a solid electrolyte membrane and an all-solid-state lithium battery.
Background
With the rapid development of new energy automobiles, lithium ion batteries occupy more and more important positions in the field of new energy, and people have higher and higher requirements on various performances of the lithium batteries. Compared with the traditional electrolyte type lithium ion battery, the all-solid-state lithium battery has the advantages that the solid electrolyte is used for replacing the electrolyte and the diaphragm, so that the battery is thinner and smaller in size; moreover, the applicable material system is more flexible, for example, metal lithium can be used as a negative electrode, so that the energy density of the whole battery is improved; in addition, electrolyte leakage is avoided, and the safety performance of the battery is improved.
The preparation of a solid electrolyte membrane is one of the key technologies of an all-solid-state lithium ion battery. Research on solid electrolytes has focused on two main areas: one is a solid electrolyte with inorganic lithium ion conductive crystal as main body, such as one disclosed in Chinese patent (CN 101103485A) with Li 1+x+y Al x Ti 2- xSi y P 3-y O 12 An inorganic solid electrolyte of a main crystal phase; the other is a solid electrolyte mainly made of organic polymer, such as a solid electrolyte prepared by using polyoxyethylene as a polymer matrix and adding nanoparticles and lithium salt, as disclosed in chinese patent (CN 102891335A). Although the inorganic solid electrolyte has high conductivity, the synthesis process is complex, high in cost, brittle and hard, and non-elastic, so that the resistance of the contact interface of the inorganic solid electrolyte and an electrode is high. The existing organic solid electrolyte has relatively low conductivity, particularly low conductivity at high temperature and poor stability.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a solid electrolyte, a solid electrolyte membrane and an all-solid-state lithium battery with high conductivity and high stability.
The purpose of the invention is realized by the following technical scheme:
a solid state electrolyte comprising, in mass percent: 10 to 90 weight percent of nanotube material, 10 to 65 weight percent of lithium salt and 0.5 to 49 weight percent of polymer.
Furthermore, the nanotube material is a one-dimensional nanotube material, and the inside of the nanotube material is negatively charged, and the outside of the nanotube material is positively charged.
Further, the lithium salt is LiPF 6 、LiAsF 6 、LiBF 4 、LiClO 4 、LiN(SO 2 CF 3 ) 2 、LiCF 3 SO 3 、LiC(SO 2 CF 3 ) 3 、LiBC 2 O 4 F 2 、LiC 4 BO 8 One or more of lithium bis (oxalato) borate, lithium isopropoxide and derivatives thereof.
Further, the polymer is one or more of polyoxyethylene, hydroxypropyl methylcellulose, polyvinylidene fluoride, polyacrylic acid, polymethyl methacrylate, polyaniline, polyethylene, polypropylene, polyamide, polycarbonate, polyester fiber, polyacrylonitrile, polysiloxane and derivatives thereof.
Furthermore, the molecular weight range of the polymer is 10000-4000000.
Further, the preparation method of the nanotube material comprises the following steps:
s1: mixing an aluminum source, an alkali solution and a surfactant to obtain a colloidal solution;
s2: and adding the colloidal solution into an autoclave for thermal reaction to obtain the nanotube material.
Further, in the step S1, one or more of a magnesium source, a silicon source, and a fourth period metal element are added in the process of preparing the colloidal solution.
Further, the aluminum source is at least one of aluminum nitrate, aluminum sulfate, aluminum silicate and aluminum chloride.
Further, the magnesium source comprises at least one of magnesium sulfate and magnesium nitrate.
Further, the silicon source is at least one of magnesium aluminum silicate and titanium oxide silicate.
Further, the fourth period metal element may be at least one of titanyl sulfate and titanyl silicate.
Further, the alkali solution is at least one of ammonia water, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like.
Further, the surfactant is at least one of sodium stearyl sulfate and sodium stearate.
Further, the molar ratio of the aluminum source to the alkali solution is 1.
Further, the addition amount of the surfactant is 0.1-2 wt% of the colloidal solution.
Further, the thermal reaction is carried out for 12 to 72 hours at the temperature of between 100 and 140 ℃.
Further, the filling amount of the autoclave is 80-90%.
In another aspect, the present invention also provides a solid electrolyte membrane prepared using the above solid electrolyte.
Further, the method for producing the solid electrolyte membrane includes the steps of: according to the mass percentage, 10-90 wt% of nanotube material, 10-65 wt% of lithium salt and 0.5-49 wt% of polymer are mixed and then the solid electrolyte membrane is obtained by adopting a solvent casting method or a hot pressing method.
Further, the solvent casting method is to add the nanotube material, lithium salt and polymer into a proper amount of solvent to mix to obtain a mixed solution, cast the mixed solution into a mold, and then perform vacuum drying to obtain the solid electrolyte membrane.
Further, the solvent is one or two of DMF, NMP, acetonitrile, ethyl acetate, DMSO, DEF, THF and water.
Further, the hot-pressing method is to directly carry out hot-pressing on the mixture of the nanotube material, the lithium salt and the polymer at the temperature of 60-150 ℃ after mixing the nanotube material, the lithium salt and the polymer according to mass percentage to obtain the solid electrolyte membrane.
Further, the thickness of the solid electrolyte membrane is 0.02mm to 0.5mm.
On the other hand, the invention also provides an all-solid-state battery, which comprises a positive pole piece coated with the positive active material and a negative pole piece coated with the negative active material, wherein the solid electrolyte membrane is arranged between the positive pole piece and the negative pole piece.
Compared with the prior art, the invention has at least the following advantages:
the solid electrolyte is prepared by blending the nanotube material, the lithium salt and the polymer, has high ionic conductivity, wide electrochemical window and good thermal stability and processability, is easy to prepare into a polymer film, has good performance, and can work in a wide temperature range and has good multiplying power and cycle performance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIG. 1 is a charge-discharge cycle chart of example 1 of the present invention;
FIG. 2 is an AC impedance plot of another embodiment of the present invention;
FIG. 3 is a cyclic voltammogram according to another embodiment of the present invention;
fig. 4 is a charge-discharge cycle diagram of example 2 of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully hereinafter with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
The invention can adopt the preparation of solid electrolyte, and the solid electrolyte has the characteristics of high ionic conductivity, wider electrochemical window, good heat resistance and easy processing, and the solid electrolyte membrane is prepared according to the solid electrolyte and used in a solid battery to prepare the all-solid-state lithium battery which has high conductivity, better multiplying power and cycle performance and can safely work in a wider temperature range.
In this embodiment, the solid electrolyte includes a nanotube material, a lithium salt, and a polymer, and the mass percentages are: nanotube material: 10wt% -90 wt%; lithium salt: 10wt% -65 wt%; polymer (b): 0.5wt% -49 wt%; the nanotube material is a one-dimensional nanotube material, the inside of the nanotube material is negatively charged, the outside of the nanotube material is positively charged, and the dissociation of lithium salt is promoted by the action of Lewis acid and alkali. The nanotube material includes aluminum metal, and further includes one or more of magnesium, silicon, and a fourth period metal element.
In this embodiment, the lithium salt is LiPF 6 、LiAsF 6 、LiBF 4 、LiClO 4 、LiN(SO 2 CF 3 ) 2 、LiCF 3 SO 3 、LiC(SO 2 CF 3 ) 3 、LiBC 2 O 4 F 2 、LiC 4 BO 8 One or more of lithium bis (oxalato) borate, lithium isopropoxide and derivatives thereof.
The polymer is one or more of PEO (polyoxyethylene), HPMC (hydroxypropyl methyl cellulose), polyvinylidene fluoride (PVDF), polyacrylic acid (PAA), (PMMA), polyaniline (PANI), polyethylene (PE), polypropylene (PP), polyamide (PA), polycarbonate (PC), polyester fiber (PET), polyacrylonitrile (PAN), polysiloxane and derivatives thereof. The molecular weight range of the polymer is 10,000-4,000,000.
The main components of the solid electrolyte are a nanotube material, a lithium salt and a polymer, wherein in the structure of the nanotube material, the outer surface containing aluminum is positive charge which can absorb anions of the lithium salt, so that lithium ions can flow in the nanotube, the crystallinity of the polymer electrolyte is reduced, the movement of molecular chain segments of the polymer is further enhanced, and an ordered inorganic material-polymer interface structure is formed, so that the ion migration rate of a solid electrolyte membrane is effectively improved, and the ionic conductivity and the cycle performance of a solid battery are improved. Meanwhile, the polymer can improve the mechanical property of the composite solid electrolyte membrane, is beneficial to improving the flexible design of the solid battery, and widens the application of the solid battery in the field of wearable equipment.
Wherein, the preparation method of the nanotube material of the invention comprises the following steps:
s1: mixing an aluminum source, an alkali solution and a surfactant to obtain a colloidal solution;
s2: and carrying out thermal reaction on the colloidal solution in a high-pressure kettle to obtain the nanotube material.
The aluminum source is at least one of aluminum nitrate, aluminum sulfate, aluminum silicate and aluminum chloride.
Furthermore, in the step S1, one or more of a magnesium source, a silicon source, and a fourth period metal element are added in the process of preparing the colloidal solution; the magnesium source is at least one of magnesium sulfate and magnesium nitrate; the silicon source is at least one of magnesium aluminum silicate and titanium oxide silicate; the fourth period metal element can be at least one of titanyl sulfate and titanyl silicate.
Further, the alkali solution is at least one of ammonia water, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like.
Wherein the molar ratio of the aluminum source to the alkali solution is 1; the addition amount of the surfactant is 0.1-2 wt% of the colloidal solution; the thermal reaction is carried out for 12 to 72 hours at the temperature of between 100 and 140 ℃.
The invention also relates to an all-solid-state battery which has high conductivity, better multiplying power and cycle performance and safe working performance in a wider temperature range by adopting the solid electrolyte.
The all-solid-state battery comprises a positive pole piece coated with a positive active material and a negative pole piece coated with a negative active material, wherein the solid electrolyte is placed between the positive pole piece and the negative pole piece, and the solid electrolyte is prepared into a solid electrolyte membrane firstly and then placed between the positive pole piece and the negative pole piece.
In order to fully exert the performance of the solid electrolyte membrane, the thickness of the solid electrolyte membrane should be controlled to be 0.02mm to 0.5mm, preferably, the thickness of the solid electrolyte membrane is 0.2mm, and another preferred thickness of the solid electrolyte membrane is 0.4mm. Thereby making it possible to ensure that the solid electrolyte membrane functions. The solid electrolyte membrane can reduce the contact interface impedance between the anode pole piece and the cathode pole piece, and has high conductivity and lower cost.
In this embodiment, the solid electrolyte membrane is prepared from the solid electrolyte by hot press molding at 60 to 150 ℃, or by a solvent casting method. The solid electrolyte membrane mainly conducts lithium ions, and can be prepared by adopting a hot-press forming method or a solvent casting method. The solid electrolyte membrane is formed by hot press molding and has high strength. The solid electrolyte membrane is prepared by forming electrolyte slurry into a membrane by a solvent casting method, and then drying the membrane at high temperature to volatilize a solvent so as to prepare the polymer electrolyte membrane. Wherein, the solvent used in the casting method is one or more of water, DMF, NMP, acetonitrile, ethyl acetate, DMSO, DEF and THF. The solid electrolyte membrane is prepared by adopting a hot-press forming or solvent casting method, has different characteristics and can be prepared according to the performance requirement of the battery.
The positive active material is one or more of lithium cobaltate, lithium manganate, nickel-manganese materials, lithium iron phosphate, nickel-cobalt-manganese, nickel-cobalt-aluminum ternary materials and sulfur-containing materials. The negative active material is one or more of lithium metal, hard carbon, soft carbon, silicon material and tin material. The selection of the anode active material and the cathode active material of the solid-state battery is wide, which shows that the application range of the solid-state electrolyte is wide, and the solid-state battery can be applied to the anode active material and the cathode active material on the market.
The method comprises the following specific embodiments:
example 1
S1: al (OH) is prepared by using aluminum nitrate and ammonia water as raw materials and adding surfactant sodium octadecyl sulfate 3 Colloid, the colloid is put in a high-pressure kettle to react for 12h at 100 ℃, and the aluminum-containing nano fiber is obtained.
S2: weighing 1g of aluminum-containing nanofiber and 0.2g of LiBF 4 0.2g of HPMC and 10g of DMSO were mixed by stirring to obtain an electrolyte solution.
S3: and drying the electrolyte solution in an oven at 60 ℃ for 20 hours in vacuum to obtain the solid electrolyte membrane.
Referring to fig. 1, taking a solid-state lithium-sulfur battery as an example, when the solid-state electrolyte membrane prepared in the first embodiment is applied to the solid-state lithium-sulfur battery, the battery performance is greatly improved when the preparation method of the first embodiment is adopted and aluminum-containing nanofibers are added, as can be seen from fig. 1, the initial capacity at 60 ℃ can reach 1310mAh/g.
Example 2
S1: the Al (OH) is prepared by using aluminum nitrate, titanyl sulfate and NaOH as raw materials and adding sodium stearate serving as a surfactant in an auxiliary way 3 /Ti(OH) 4 Colloid, the colloid is put in a high-pressure kettle to react for 36h at 140 ℃, and the aluminum and titanium containing nano fiber is obtained.
S2: weighing 1g of the aluminum-titanium-containing nano fiber and 0.4g of LiAsF 6 0.02g of PEO (1,000,000 molecular weight), 20g of acetonitrile were mixed with stirring to obtain an electrolyte solution.
S3: and drying the electrolyte solution in an oven at 50 ℃ for 5 hours in vacuum to obtain the solid electrolyte membrane.
Referring to FIG. 2, the ionic conductivity of the electrolyte at 25 ℃ was calculated to be 2 × 10 according to the AC impedance results -4 S cm -1 . According to the cyclic voltammetry result, the electrolyte still has higher lithium decomposition voltage of more than 4.3V at 60 ℃. At the same time, assembling into LiFePO 4 The capacity retention rate of the/C soft package battery subjected to 3000 cycles under the conditions of 60 ℃ and 5C charge and discharge can reach more than 85%.
Example 3
S1: using aluminium sulfate, magnesium sulfate and ammonia water as raw materials, and adding surfactant sodium stearate as auxiliary material to prepare the Al (OH) 3 /Mg(OH) 2 Colloid, the colloid is put in a high-pressure kettle to react for 72 hours at 110 ℃ to obtain the aluminum-magnesium-containing nano tube.
S2: weighing 1g of the aluminum-magnesium-containing nanotube and 1g of LiCF 3 SO 3 And 1.3g of PMMA, and the mixture is subjected to hot press molding at 80 ℃ after blending and grinding to obtain the solid electrolyte membrane. Of these, PMMA has a molecular weight of 4,000,000.
Referring to FIG. 3, the ionic conductivity of the electrolyte at 25 ℃ was calculated to be 1 × 10 according to the AC impedance results -4 S cm -1 According to the cyclic voltammetry result, the electrolyte has higher power for decomposing lithiumPressure, over 5.0V. Assembled into LiFePO 4 The specific capacity of the Li button cell can reach 159mAh g at 25 DEG C -1 . According to the cyclic voltammetry result, the electrolyte still has a high lithium decomposition voltage of more than 4.7V at 80 ℃.
Comparative example 1
Comparative example 1 is different from example 1 in that the aluminum-containing nanofibers are not added in the preparation of the electrolyte solution in the step S2, and the other preparation conditions are the same as those of example 1.
Referring to fig. 1, taking a solid-state lithium-sulfur battery as an example, as can be seen from fig. 1, the first capacity exertion at 60 ℃ reaches 1190mAh/g, which is significantly reduced in example 1, and as can be seen from fig. 1, the capacity of example 1 is kept more stable during 100 cycles of charge and discharge, while the capacity retention rate of comparative example 1 is only about half of that of example 1, which shows that the addition of nanotube material (aluminum-containing nanofibers) in the solid-state electrolyte can significantly improve the electrochemical performance of the solid-state lithium-sulfur battery.
Comparative example 2
Comparative example 2 differs from example 2 in that the nanotube material used is commercially available halloysite nanotubes, and the preparation conditions are otherwise the same as in example 2.
Referring to fig. 4, it can be seen from fig. 4 that when a halloysite nanotube is used as a raw material to prepare a solid electrolyte, it is finally assembled into LiFePO 4 The capacity retention rate of a/C soft package battery subjected to 2000 cycles under the conditions of 60 ℃ and 5C charging and discharging is only about 82%, and compared with the example 2, the cycle capacity retention rate is greatly reduced, probably because a natural nanotube material is adopted in a commercial halloysite nanotube, the distribution of positive and negative charges inside and outside the nanotube is disordered, and the self-made nanotube material (containing aluminum and titanium nanofibers) in the example 2 has negative charges inside the nanotube and positive charges outside the nanotube, so that the ion migration rate of a solid electrolyte membrane can be effectively improved, and the ion conductivity and the solid battery cycle performance are improved.
Compared with the prior art, the invention has at least the following advantages: the composite polymer electrolyte is prepared by blending a nanotube material, lithium salt and a small amount of polymer, has high ionic conductivity, wide electrochemical window and good thermal stability and processability, is easy to prepare into a polymer film, and can be prepared by a conventional solvent casting method or a hot-pressing method. The solid electrolyte membrane prepared by the solid electrolyte has good performance, and the all-solid-state lithium battery assembled by the electrolyte can work in a wider temperature range and has good multiplying power and cycle performance.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A solid electrolyte comprising, in mass percent: 10 to 90 weight percent of nanotube material, 10 to 65 weight percent of lithium salt and 0.5 to 49 weight percent of polymer.
2. The solid-state electrolyte of claim 1, wherein the nanotube material is a one-dimensional nanotube material having a negative charge inside the tube and a positive charge outside the tube.
3. The solid electrolyte of claim 1, wherein the lithium salt is LiPF 6 、LiAsF 6 、LiBF 4 、LiClO 4 、LiN(SO 2 CF 3 ) 2 、LiCF 3 SO 3 、LiC(SO 2 CF 3 ) 3 、LiBC 2 O 4 F 2 、LiC 4 BO 8 One or more of lithium bis (oxalato) borate, lithium isopropoxide and derivatives thereof.
4. The solid state electrolyte of claim 1, wherein the polymer is one or more of polyethylene oxide, hydroxypropyl methylcellulose, polyvinylidene fluoride, polyacrylic acid, polymethyl methacrylate, polyaniline, polyethylene, polypropylene, polyamide, polycarbonate, polyester fiber, polyacrylonitrile, polysiloxane, and derivatives thereof.
5. The solid-state electrolyte of claim 2, wherein the nanotube material is prepared by a method comprising the steps of:
s1: mixing an aluminum source with an alkali solution and a surfactant to obtain a colloidal solution;
s2: and carrying out thermal reaction on the colloidal solution in a high-pressure kettle to obtain the nanotube material.
6. The solid electrolyte of claim 5, wherein in step S1, one or more of a magnesium source, a silicon source, and a fourth period metal element are further added during the preparation of the colloidal solution.
7. The solid-state electrolyte of claim 5, wherein the aluminum source is at least one selected from the group consisting of aluminum nitrate, aluminum sulfate, aluminum silicate, and aluminum chloride.
8. A solid electrolyte membrane produced using the solid electrolyte according to any one of claims 1 to 7.
9. An all-solid-state battery comprising a positive electrode plate coated with a positive electrode active material and a negative electrode plate coated with a negative electrode active material, wherein the solid electrolyte membrane according to claim 8 is provided between the positive electrode plate and the negative electrode plate.
10. The all-solid battery according to claim 9, wherein the solid electrolyte membrane has a thickness of 0.02mm to 0.5mm.
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