CN115954530B - Solid electrolyte, solid electrolyte membrane and all-solid lithium battery - Google Patents
Solid electrolyte, solid electrolyte membrane and all-solid lithium battery Download PDFInfo
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- CN115954530B CN115954530B CN202211736626.XA CN202211736626A CN115954530B CN 115954530 B CN115954530 B CN 115954530B CN 202211736626 A CN202211736626 A CN 202211736626A CN 115954530 B CN115954530 B CN 115954530B
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 69
- 239000012528 membrane Substances 0.000 title claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 20
- 239000007787 solid Substances 0.000 title claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 41
- 239000002071 nanotube Substances 0.000 claims abstract description 41
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 20
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 16
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- -1 polyoxyethylene, hydroxypropyl Polymers 0.000 claims description 16
- 239000000084 colloidal system Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 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
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 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
- 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
- 235000010979 hydroxypropyl methyl cellulose Nutrition 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
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910015015 LiAsF 6 Inorganic materials 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
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- 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 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims 1
- 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
- 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
- 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
- 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
- 150000002500 ions Chemical class 0.000 description 5
- 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
- 229920003171 Poly (ethylene oxide) Polymers 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
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 229910003480 inorganic solid Inorganic materials 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
- 238000000465 moulding Methods 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
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 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
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910052621 halloysite Inorganic materials 0.000 description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 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
- 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 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
- 239000005518 polymer electrolyte 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
- 229910052719 titanium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910015013 LiAsF Inorganic materials 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
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 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
- 239000003054 catalyst Substances 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
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 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
- 238000001453 impedance spectrum Methods 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
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture 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
- 238000003756 stirring Methods 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
Classifications
-
- 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
Abstract
The invention relates to a solid electrolyte, a solid electrolyte membrane and an all-solid lithium battery, wherein the solid electrolyte comprises the following components in percentage by mass: the invention prepares a solid electrolyte through blending nanotube material, lithium salt and polymer, wherein the solid electrolyte has high ionic conductivity, wide electrochemical window, good thermal stability and processability, and is easy to prepare polymer film, the solid electrolyte film prepared by the solid electrolyte has good performance, and the all-solid 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 lithium battery.
Background
With the rapid development of new energy automobiles, lithium ion batteries occupy an increasingly important position in the new energy field, and various performance requirements of people on the lithium batteries are also higher. Compared with the traditional lithium ion battery using electrolyte, the all-solid-state lithium battery has the advantages that the electrolyte and the diaphragm are replaced by the solid electrolyte, so that the battery is thinner and smaller in volume; the applicable material system is more flexible, for example, lithium metal 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 all-solid lithium ion batteries. Research into solid electrolytes has focused mainly on two aspects: one is a solid electrolyte mainly comprising inorganic lithium ion conductive crystals, such as a solid electrolyte with Li disclosed in Chinese patent (CN 101103485A) 1+x+y Al x Ti 2- xSi y P 3-y O 12 An inorganic solid electrolyte of a main crystal phase; another is a solid electrolyte mainly composed of an organic polymer, such as one disclosed in chinese patent (CN 102891335 a) which uses polyoxyethylene as a polymer matrix and incorporates nanoparticles and lithium salts. Although the inorganic solid electrolyte has higher conductivity, the inorganic solid electrolyte has complex synthesis process, high cost, brittleness, hardness and no elasticity, and causes large interface impedance between the inorganic solid electrolyte and an electrode. The existing organic solid electrolyte has relatively low conductivity, particularly low conductivity and poor stability at high temperature.
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 lithium battery which are high in conductivity and high in stability.
The aim 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.
Further, the nanotube material is a one-dimensional nanotube material, 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 bisoxalato 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, polypropylene cyanide, polysiloxane and derivatives thereof.
Further, 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 colloid solution;
s2: and adding the colloid 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 colloid solution.
Further, the aluminum source comprises 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 titanyl 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 comprises at least one of sodium stearyl sulfate and sodium stearate.
Further, the molar ratio of the aluminum source to the alkali solution is 1:3-1:5.
Further, the addition amount of the surfactant is 0.1-2 wt% of the colloidal solution.
Further, the thermal reaction is carried out for 12-72 h at 100-140 ℃.
Further, the filling amount of the autoclave is 80% -90%.
On the other hand, the invention also provides a solid electrolyte membrane, which is prepared from the solid electrolyte.
Further, the preparation method of the solid electrolyte membrane comprises the following steps: according to the mass percentage, 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 are selected and 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, the lithium salt and the polymer into a proper amount of solvent to be mixed 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.
And further, the hot pressing method is to mix the nanotube material, the lithium salt and the polymer according to mass percent and then directly hot press the mixture at 60-150 ℃ to obtain the solid electrolyte membrane.
Further, the thickness of the solid electrolyte membrane is 0.02 mm-0.5 mm.
On the other hand, the invention also provides an all-solid-state battery, which comprises 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 is arranged between the positive electrode plate and the negative electrode plate.
Compared with the prior art, the invention has at least the following advantages:
the solid electrolyte is prepared by blending nanotube materials, lithium salt and polymers, has high ionic conductivity, wide electrochemical window, good thermal stability and processability, and is easy to prepare into polymer films.
Drawings
In order to more clearly illustrate 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 therefore 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 charge-discharge cycle chart of example 1 of the present invention;
FIG. 2 is an alternating current impedance spectrum of another embodiment of the present invention;
FIG. 3 is a cyclic voltammogram of another embodiment of the present invention;
fig. 4 is a charge-discharge cycle chart of example 2 of the present invention.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. The drawings illustrate preferred embodiments of the invention. 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 be used for preparing the solid electrolyte, and the solid electrolyte has the characteristics of high ion conductivity, wider electrochemical window, good heat resistance and easy processing, and the solid electrolyte film is prepared according to the solid electrolyte and used in a solid battery to prepare an all-solid 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 thereof are: nanotube material: 10-90 wt%; lithium salt: 10-65 wt%; and (2) polymer: 0.5 to 49 weight percent; the nanotube material is 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 Lewis acid-base effect. 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 bisoxalato borate, lithium isopropoxide and derivatives thereof.
The polymer is one or more of PEO (polyoxyethylene), HPMC (hydroxypropyl methylcellulose), polyvinylidene fluoride (PVDF), polyacrylic acid (PAA), (PMMA), polyaniline (PANI), polyethylene (PE), polypropylene (PP), polyamide (PA), polycarbonate (PC), polyester fiber (PET), polypropylene cyanide (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 nanotube material, lithium salt and polymer, wherein the outside of the nanotube material containing aluminum is positively charged in the structure of the nanotube material, so that lithium ions can flow in the tube, thereby reducing the crystallinity of the polymer electrolyte, further enhancing the movement of polymer molecular chain segments, forming an ordered inorganic material-polymer interface structure, effectively improving the ion migration rate of the solid electrolyte membrane, and improving the ion conductivity and the cycle performance of the solid battery. 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.
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 colloid solution;
s2: and carrying out thermal reaction on the colloid solution in an autoclave to obtain the nanotube material.
Wherein the aluminum source comprises at least one of aluminum nitrate, aluminum sulfate, aluminum silicate and aluminum chloride.
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 colloid solution; the magnesium source comprises at least one of magnesium sulfate and magnesium nitrate; the silicon source is at least one of magnesium aluminum silicate and titanyl 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 1:3-1:5; the addition amount of the surfactant is 0.1-2 wt% of the colloid solution; the thermal reaction is carried out for 12-72 h at 100-140 ℃.
The invention also relates to an all-solid-state battery which has high conductivity, good multiplying power and cycle performance and safe working performance in a wider temperature range by adopting the solid-state electrolyte.
The all-solid-state battery comprises 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 is arranged between the positive electrode plate and the negative electrode plate, and the solid electrolyte is required to be prepared into a solid electrolyte membrane firstly and then arranged between the positive electrode plate and the negative electrode plate.
In order to give full play to 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, the thickness of the solid electrolyte membrane is 0.4mm. Thereby ensuring the functioning of the solid electrolyte membrane. The solid electrolyte membrane can reduce the contact interface impedance between the positive pole piece and the negative 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 60-150 ℃ or by a solvent casting method. The solid electrolyte membrane mainly has the function of conducting lithium ions, and can be prepared by adopting a hot press molding method or a solvent casting method. The solid electrolyte membrane is formed by hot press molding and has the characteristic of high strength. The solid electrolyte membrane is prepared by forming a film of electrolyte slurry by solvent casting, and then drying at high temperature to volatilize the solvent. Wherein the solvent used in the casting method is one or more of water, DMF, NMP, acetonitrile, ethyl acetate and DMSO, DEF, THF. The solid electrolyte membrane is prepared by adopting hot press molding or solvent casting, has different characteristics and can be prepared according to the performance requirements of the battery.
The positive electrode active material is one or more of lithium cobaltate, lithium manganate, nickel manganese material, lithium iron phosphate, nickel cobalt manganese, nickel cobalt aluminum ternary material and sulfur-containing material. The negative electrode active material is one or more of lithium metal, hard carbon, soft carbon, silicon material and tin material. The solid-state battery of the invention has wide selection of the positive electrode active material and the negative electrode active material, which indicates that the application of the solid-state electrolyte of the invention has wide application range and is applicable to both the positive electrode active material and the negative electrode active material on the market.
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 in an auxiliary way 3 And (3) placing the colloid in an autoclave to react for 12 hours at the temperature of 100 ℃ to obtain the aluminum-containing nanofiber.
S2: by weighing 1g of aluminum-containing nanofiber and 0.2g of LiBF 4 0.2g HPMC and 10g DMSO were mixed and stirred to obtain an electrolyte solution.
S3: the electrolyte solution was dried in an oven at 60 ℃ for 20 hours under vacuum to obtain a solid electrolyte membrane.
Referring to fig. 1, taking a solid-state lithium sulfur battery as an example, the solid-state electrolyte membrane prepared in the first embodiment is applied to the solid-state lithium sulfur battery, and when the preparation method in the first embodiment is adopted and the aluminum-containing nanofiber is added, the battery performance is greatly improved, and as can be seen from fig. 1, the first capacity can reach 1310mAh/g at 60 ℃.
Example 2
S1: al (OH) is prepared by using aluminum nitrate, titanyl sulfate and NaOH as raw materials and adding surfactant sodium stearate in an auxiliary way 3 /Ti(OH) 4 And (3) placing the colloid into an autoclave to react for 36 hours at 140 ℃ to obtain the aluminum-and titanium-containing nanofiber.
S2: 1g of the aluminum-containing and titanium-containing nanofiber and 0.4g of LiAsF were weighed 6 0.02g PEO (1,000,000 molecular weight), 20g acetonitrile were blended with stirring to obtain an electrolyte solution.
S3: the electrolyte solution was dried in an oven at 50 ℃ for 5 hours under vacuum to obtain a solid electrolyte membrane.
Referring to FIG. 2, the ionic conductivity of the electrolyte at 25℃was calculated to be 2X 10 based on the AC impedance results -4 S cm -1 . The electrolyte still has a high voltage exceeding 4.3V for lithium decomposition at 60 ℃ according to the cyclic voltammetry result. At the same time, assembled into LiFePO 4 The capacity retention rate of the soft package battery/C can reach more than 85% after 3000 times of circulation under the condition of 60 ℃ and 5C charge and discharge.
Example 3
S1: aluminum sulfate, magnesium sulfate and ammonia water are used as raw materials, and a surfactant sodium stearate is added in an auxiliary way to prepare the aluminum-containing (OH) catalyst 3 /Mg(OH) 2 And (3) placing the colloid into an autoclave to react for 72 hours at the temperature of 110 ℃ to obtain the aluminum-magnesium-containing nano tube.
S2: weighing 1g of the aluminum-containing and magnesium-containing nanotubes and 1g of LiCF 3 SO 3 1.3g PMMA, blending and grinding, and hot-pressing at 80 ℃ to obtain the solid electrolyte membrane. Wherein PMMA is 4,000,000 molecular weight.
Referring to FIG. 3, the ionic conductivity of the electrolyte at 25℃was calculated to be 1X 10 based on the AC impedance results -4 S cm -1 The electrolyte has a high decomposition voltage for lithium, exceeding 5.0V, according to the cyclic voltammetry result. Assembled into LiFePO 4 Li button type electric deviceThe specific capacity of the pool can reach 159mAh g at 25 DEG C -1 . The electrolyte still has a high decomposition voltage for lithium at 80 ℃ which exceeds 4.7V according to the cyclic voltammetry result.
Comparative example 1
Comparative example 1 is different from example 1 in that the step S2 does not add aluminum-containing nanofibers during the preparation of the electrolyte solution, and the other preparation conditions are the same as example 1.
Referring to fig. 1, taking a solid-state lithium sulfur battery as an example, it can be seen from fig. 1 that the first capacity at 60 ℃ reaches 1190mAh/g, which is significantly lower than that of example 1, and that the capacity of example 1 remains more stable during 100 cycles of charge and discharge, while the capacity retention rate of comparative example 1 is only about half that of example 1, and it can be seen that the electrochemical performance of the solid-state lithium sulfur battery can be significantly improved by adding a nanotube material (aluminum-containing nanofiber) into the solid-state electrolyte.
Comparative example 2
Comparative example 2 was different from example 2 in that the nanotube material was a commercially available halloysite nanotube, and the other preparation conditions were the same as example 2.
Referring to fig. 4, it can be seen from fig. 4 that when preparing a solid electrolyte using halloysite nanotubes as a raw material, it is finally assembled into LiFePO 4 The capacity retention rate of the soft-packed/C battery is only about 82% after 2000 cycles at 60 ℃ and 5C charge and discharge, and compared with the method in example 2, the cycle capacity retention rate is greatly reduced, and the method is probably because the commercial halloysite nanotube is a natural nanotube material, the positive and negative charge distribution inside and outside the tube is disordered, and the self-made nanotube material (aluminum-containing and titanium-containing nanofibers) in example 2 has negative charges in the tube and positive charges outside the tube, so that the ion migration rate of the solid electrolyte membrane can be effectively improved, and the ion conductivity and the cycle performance of the solid battery 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, and the polymer has high ionic conductivity, wide electrochemical window, good thermal stability and processability, is easy to prepare into a polymer film, can be prepared by a conventional solvent casting method, and can also be molded by a hot pressing method. The solid electrolyte membrane prepared by the solid electrolyte has good performance, and the all-solid lithium battery assembled by the electrolyte can work in a wider temperature range and has good multiplying power and cycle performance.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (7)
1. 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; the nanotube material is a one-dimensional nanotube material, the inside of the nanotube material is negatively charged, and the outside of the nanotube material is positively charged;
the preparation method of the nanotube material comprises the following steps:
s1: mixing an aluminum source with an alkali solution and a surfactant to obtain a colloid solution;
s2: carrying out thermal reaction on the colloid solution in an autoclave to obtain the nanotube material;
in the step S1, one or more of a magnesium source, a silicon source and a fourth-period metal element are also added in the process of preparing the colloid solution;
the alkali solution is at least one of ammonia water, sodium hydroxide, potassium hydroxide and lithium hydroxide;
the molar ratio of the aluminum source to the alkali solution is 1:3-1:5.
2. The solid state 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 bisoxalato borate and lithium isopropoxide.
3. The solid state electrolyte of claim 1 wherein 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.
4. The solid state electrolyte of claim 1 wherein the aluminum source is at least one of aluminum nitrate, aluminum sulfate, aluminum silicate, aluminum chloride.
5. A solid electrolyte membrane prepared using the solid electrolyte of any one of claims 1 to 4.
6. An all-solid-state battery comprising a positive electrode sheet coated with a positive electrode active material and a negative electrode sheet coated with a negative electrode active material, the solid electrolyte membrane of claim 5 being provided between the positive electrode sheet and the negative electrode sheet.
7. The all-solid battery according to claim 6, wherein the thickness of the solid electrolyte membrane is 0.02mm to 0.5mm.
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