CN100583543C - Lithium ion conductive solid electrolyte, method for producing same, solid electrolyte for lithium secondary battery using same, and all-solid-state lithium battery using same - Google Patents
Lithium ion conductive solid electrolyte, method for producing same, solid electrolyte for lithium secondary battery using same, and all-solid-state lithium battery using same Download PDFInfo
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- CN100583543C CN100583543C CN200680001957A CN200680001957A CN100583543C CN 100583543 C CN100583543 C CN 100583543C CN 200680001957 A CN200680001957 A CN 200680001957A CN 200680001957 A CN200680001957 A CN 200680001957A CN 100583543 C CN100583543 C CN 100583543C
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- lithium
- sulfide
- solid electrolyte
- boron
- ion
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 68
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 27
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052796 boron Inorganic materials 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims description 46
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 33
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 30
- 239000005864 Sulphur Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 23
- ZVTQDOIPKNCMAR-UHFFFAOYSA-N sulfanylidene(sulfanylideneboranylsulfanyl)borane Chemical compound S=BSB=S ZVTQDOIPKNCMAR-UHFFFAOYSA-N 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000011521 glass Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 14
- 239000002241 glass-ceramic Substances 0.000 claims description 13
- 229910052738 indium Inorganic materials 0.000 claims description 13
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 13
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 13
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 13
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052733 gallium Inorganic materials 0.000 claims description 10
- 229910052732 germanium Inorganic materials 0.000 claims description 10
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 9
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 7
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 4
- 150000004763 sulfides Chemical class 0.000 claims 1
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000470 constituent Substances 0.000 abstract description 8
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract 2
- 239000011593 sulfur Substances 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 description 33
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 15
- 239000003960 organic solvent Substances 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 12
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Natural products O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 7
- -1 hydrogen lithium sulfide Chemical class 0.000 description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003708 ampul Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000005387 chalcogenide glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000003495 polar organic solvent Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910013184 LiBO Inorganic materials 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- IKJFYINYNJYDTA-UHFFFAOYSA-N dibenzothiophene sulfone Chemical compound C1=CC=C2S(=O)(=O)C3=CC=CC=C3C2=C1 IKJFYINYNJYDTA-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- BSJWDQYZFBYNIM-UHFFFAOYSA-N 1,3,4,5-tetramethylpyrrolidin-2-one Chemical compound CC1C(C)N(C)C(=O)C1C BSJWDQYZFBYNIM-UHFFFAOYSA-N 0.000 description 1
- NCNWTBAWLAFYDR-UHFFFAOYSA-N 1,6-dimethylpiperidin-2-one Chemical class CC1CCCC(=O)N1C NCNWTBAWLAFYDR-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- BNXZHVUCNYMNOS-UHFFFAOYSA-N 1-butylpyrrolidin-2-one Chemical compound CCCCN1CCCC1=O BNXZHVUCNYMNOS-UHFFFAOYSA-N 0.000 description 1
- MXEOFTCIEDUHCX-UHFFFAOYSA-N 1-cyclohexylazepan-2-one Chemical compound O=C1CCCCCN1C1CCCCC1 MXEOFTCIEDUHCX-UHFFFAOYSA-N 0.000 description 1
- VUQMOERHEHTWPE-UHFFFAOYSA-N 1-ethylpiperidin-2-one Chemical class CCN1CCCCC1=O VUQMOERHEHTWPE-UHFFFAOYSA-N 0.000 description 1
- GGYVTHJIUNGKFZ-UHFFFAOYSA-N 1-methylpiperidin-2-one Chemical class CN1CCCCC1=O GGYVTHJIUNGKFZ-UHFFFAOYSA-N 0.000 description 1
- GVDQKJQFVPXADH-UHFFFAOYSA-N 1-propan-2-ylpiperidin-2-one Chemical class CC(C)N1CCCCC1=O GVDQKJQFVPXADH-UHFFFAOYSA-N 0.000 description 1
- GHELJWBGTIKZQW-UHFFFAOYSA-N 1-propan-2-ylpyrrolidin-2-one Chemical compound CC(C)N1CCCC1=O GHELJWBGTIKZQW-UHFFFAOYSA-N 0.000 description 1
- DRYYJQYUHPRVBN-UHFFFAOYSA-N 3-ethyl-1-methylpiperidin-2-one Chemical class CCC1CCCN(C)C1=O DRYYJQYUHPRVBN-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 229910010199 LiAl Inorganic materials 0.000 description 1
- 229910010093 LiAlO Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010835 LiI-Li2S-P2S5 Inorganic materials 0.000 description 1
- 229910010833 LiI-Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910010823 LiI—Li2S—B2S3 Inorganic materials 0.000 description 1
- 229910010840 LiI—Li2S—P2S5 Inorganic materials 0.000 description 1
- 229910010855 LiI—Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- 208000036142 Viral infection Diseases 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- GFLFKGYNEFFWTR-UHFFFAOYSA-N lithium;2-(methylamino)butanoic acid Chemical compound [Li].CCC(NC)C(O)=O GFLFKGYNEFFWTR-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IMNDHOCGZLYMRO-UHFFFAOYSA-N n,n-dimethylbenzamide Chemical compound CN(C)C(=O)C1=CC=CC=C1 IMNDHOCGZLYMRO-UHFFFAOYSA-N 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229960001930 valpromide Drugs 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Images
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 present invention provides a lithium ion conductive solid electrolyte which exhibits high lithium ion conductivity even at room temperature, is difficult to oxidize, has few problems of toxicity, contains lithium , boron (B), sulfur (S) and oxygen (O) as constituent components, and has a ratio of sulfur to oxygen (O/S) of 0.01 to 1.43.
Description
Technical field
The present invention relates to: contain lithium, boron, sulphur and oxygen as constituent, have the lithium-ion-conducting solid electrolyte of the ratio of specific sulphur and oxygen; Contain lithium, boron, sulphur and oxygen element as constituent, have the lithium-ion-conducting solid electrolyte at specific X-ray diffraction peak; Lithium sulfide (Li
2S): boron sulfide (B
2S
3): with Li
aMO
bThe mole % ratio of the compound of expression has with X (100-Y): (1-X) lithium-ion-conducting solid electrolyte of the composition represented of (100-Y): Y; [wherein, M represents to be selected from the element in phosphorus, silicon, aluminium, boron, sulphur, germanium, gallium, the indium, and a and b represent 1～10 number independently, and X represents 0.5～0.9 number, and Y represents 0.5～30 mole of % with the chalcogenide glass of this composition.] manufacture method of heat treated solid electrolyte under 100～350 ℃; The lithium-ion-conducting solid electrolyte that utilizes this manufacture method to obtain; The secondary lithium batteries solid electrolyte of these solid electrolytes and the all-solid lithium battery that uses this secondary cell to form have been used with solid electrolyte.
Background technology
In recent years, to carrying information terminal, carry e-machine, the household small-size electrical storage device, being that the demand of lithium secondary battery of high performance used in the two-wheeled motorcycle, electric automobile, compound electric automobile etc. of power source etc. increases with the motor.
Here, so-called secondary cell be meant can charging and discharging battery.
In addition, along with the expansion of the purposes that can use, require the raising and the high performance of the further fail safe of secondary cell.
Inorganic solid electrolyte is an incombustibility at it in nature, is to compare the higher material of fail safe with used usually organic class electrolyte.
But owing to compare with organic class electrolyte, therefore electrochemical poor-performing needs the further performance of raising inorganic solid electrolyte.
In the past, the electrolyte that at room temperature demonstrates high lithium-ion-conducting was limited to organic class electrolyte basically.
But therefore organic class electrolyte in the past is flammable owing to contain organic solvent.
So, in the ionic conductivity material that will contain organic solvent uses as the electrolyte of battery, the danger of may or catch fire of leakage is arranged.
In addition, this organic class electrolyte is owing to be liquid, so conductive lithium ion not only, but also the conductive equilibrium ion, so the lithium ion mobility is below 1.
At this kind problem, carried out the research of various sulfide-based solid electrolytes in the past.
For example, in the eighties in 20th century,, found to have 10 as lithium-ion-conducting solid electrolyte with high ion-conductivity
-3The chalcogenide glass of the ionic conductivity of S/cm, for example LiI-Li
2S-P
2S
5, LiI-Li
2S-B
2S
3, LiI-Li
2S-SiS
2Deng.
But in order to improve ionic conductance, these solid electrolytes are doped with lithium iodide, therefore are subjected to electrochemical oxidation easily, are difficult to be formed in the all-solid lithium battery of the above action of 3V.
In addition, the phosphorus pentasulfide (P that uses at raw material as described solid electrolyte
2S
5) in virose problem, bring difficulty in industrial meeting.
Summary of the invention
The present invention is under this kind situation, and purpose is, a kind of lithium-ion-conducting solid electrolyte is provided, and it at room temperature also can demonstrate high lithium ion conductivity, is difficult to oxidizedly, and the problem of toxicity also seldom; The manufacture method of this solid electrolyte; The solid electrolyte that utilizes this manufacture method to obtain; And used the secondary lithium batteries solid electrolyte of this solid electrolyte; And the all-solid lithium battery that uses this secondary cell to form with solid electrolyte.
The inventor etc. further investigate repeatedly in order to reach affiliated purpose, found that, will reached with general formula Li by lithium sulfide, boron sulfide
aMO
bAfter the raw mix frit reaction that the compound of expression constitutes, by carrying out chilling, just can obtain the lithium-ion-conducting solid electrolyte of high ion-conductivity, thereby finish the present invention.
That is, the invention provides:
1. a lithium-ion-conducting solid electrolyte is characterized in that, as constituent, contains lithium (Li), boron (B), sulphur (S) and oxygen (O) element, and the ratio of sulphur and oxygen element (O/S) is 0.01～1.43.
2. a lithium-ion-conducting solid electrolyte is characterized in that, lithium sulfide (Li
2S): boron sulfide (B
2S
3): with Li
aMO
bThe mole % ratio of the compound of expression has with X (100-Y): (1-X) composition represented of (100-Y): Y.
[wherein, M represents to be selected from the element in phosphorus (P), silicon (Si), aluminium (Al), boron (B), sulphur (S), germanium (Ge), gallium (Ga), the indium (In), and a and b represent 1～10 number independently, and X represents 0.5～0.9 number, and Y represents 0.5～30 mole of %.]
3. lithium-ion-conducting solid electrolyte, it is characterized in that, as constituent, contain lithium (Li), boron (B), sulphur (S) and oxygen (O) element, (among CuK α: the λ=0.15418nm), has diffraction maximum at X-ray diffraction at 2 θ=19.540 ± 0.3deg, 28.640 ± 0.3deg and 29.940 ± 0.3deg place.
4. a method for producing lithium ion conductive solid electrolyte is characterized in that, with lithium sulfide (Li
2S): boron sulfide (B
2S
3): with Li
aMO
bThe mole % of the compound of expression is than for X (100-Y): (1-X) the sulfide-based glass of the composition represented of (100-Y): Y is heat-treated under 100～350 ℃.
[wherein, M represents to be selected from the element in phosphorus (P), silicon (Si), aluminium (Al), boron (B), sulphur (S), germanium (Ge), gallium (Ga), the indium (In), and a and b represent 1～10 number independently, and X represents 0.5～0.9 number, and Y represents 0.5～30 mole of %.]
5. according to the method for producing lithium ion conductive solid electrolyte of record in described 4, wherein, with general formula Li
aMO
bThe compound of expression is selected from lithium metasilicate, lithium borate, lithium phosphate.
6. according to the method for producing lithium ion conductive solid electrolyte of record in described 4 or 5, wherein, replace boron sulfide, and use the boron of suitable mol ratio and the mixture of element sulphur.
7. one kind is utilized any lithium-ion-conducting solid electrolyte that the manufacture method of being put down in writing obtains in described 4～6.
8. one kind is used any secondary lithium batteries solid electrolyte that the lithium-ion-conducting solid electrolyte of being put down in writing forms in described 1～3 or 7.
9. all-solid lithium battery that the secondary lithium batteries solid electrolyte that uses record in described 8 forms.
Lithium-ion-conducting solid electrolyte of the present invention is an inoganic solids owing to have the decomposition voltage more than 10V at least, is incombustibility therefore, when maintenance lithium ion mobility is 1 characteristic, at room temperature demonstrates 10
-3High lithium-ion-conducting about S/cm.
So, very be suitable as the solid electrolyte material of lithium battery.
In addition, used the all-solid lithium battery of lithium-ion-conducting solid electrolyte of the present invention can not only the metric density height, good aspect fail safe and charge and discharge cycles operating characteristic, and in used raw material, do not have high toxicity.
Description of drawings
Fig. 1 is the figure of X-ray diffraction spectrogram of the powdered sample of the frit reaction thing (before the heat treatment) that obtains among the embodiment 1 of expression and heat treatment thing.
Fig. 2 is the figure of cyclic voltammetry curve of the heat treatment thing of expression embodiment 6.
Fig. 3 is the figure of the charge-discharge characteristic of the battery that obtains among the embodiment 7 of expression.
Embodiment
Lithium-ion-conducting solid electrolyte of the present invention contains lithium, boron, sulphur and oxygen element as constituent, and the ratio of sulphur and oxygen element (O/S) is 0.01～1.43, and is preferred 0.03～1.2, and more preferably 0.05～1.0.
Described lithium-ion-conducting solid electrolyte comprises: with frit reaction thing chilling described later and sulfide-based glass; The sulfide-based sintered glass ceramics that this glass heat processing is got; And the mixture of the ratio arbitrarily of sulfide-based glass and sulfide-based sintered glass ceramics.
In addition, lithium-ion-conducting solid electrolyte of the present invention is the lithium-ion-conducting solid electrolyte with following feature, that is, and and lithium sulfide (Li
2S): boron sulfide (B
2S
3): with Li
aMO
bThe mole % ratio of the compound of expression has with X (100-Y): (1-X) composition represented of (100-Y): Y.
[wherein, M represents to be selected from the element in phosphorus (P), silicon (Si), aluminium (Al), boron (B), sulphur (S), germanium (Ge), gallium (Ga), the indium (In), and a and b represent 1～10 number independently, and X represents 0.5～0.9 number, and Y represents 0.5～30 mole of %.]
Described lithium-ion-conducting solid electrolyte comprises: with frit reaction thing chilling described later and sulfide-based glass; The sulfide-based sintered glass ceramics that this glass heat processing is got; And the mixture of the ratio arbitrarily of sulfide-based glass and sulfide-based sintered glass ceramics.
In addition, lithium-ion-conducting solid electrolyte of the present invention is as constituent, contain lithium, boron, sulphur and oxygen element, (among CuK α: the λ=0.15418nm), have diffraction maximum at 2 θ=19.540 ± 0.3deg, 28.640 ± 0.3deg and 29.940 ± 0.3deg place at X-ray diffraction.
Described lithium-ion-conducting solid electrolyte comprises the sulfide-based sintered glass ceramics that sulfide-based glass heat processing described later is got.
And, in lithium-ion-conducting solid electrolyte of the present invention,, can also add the element that is selected from silicon, phosphorus, aluminium, germanium, gallium, the indium as other constituent.
Lithium-ion-conducting solid electrolyte of the present invention can be by with lithium sulfide: the boron of boron sulfide or the mol ratio suitable with boron sulfide and the mixture of element sulphur: with Li
aMO
bThe mole % of the compound of expression is than being X (100-Y): (1-X) (100-Y): after the raw mix frit reaction that Y constituted, carry out chilling and make.
M, a, b, X and Y are with described identical.
In addition, lithium-ion-conducting solid electrolyte of the present invention can be by with lithium sulfide: the boron of boron sulfide or the mol ratio suitable with boron sulfide and the mixture of element sulphur: with Li
aMO
bThe mole % of the compound of expression is than being X (100-Y): (1-X) (100-Y): after the raw mix frit reaction that Y constituted, carry out chilling, make 100～350 ℃ of following heat treatments then.
Lithium sulfide used among the present invention is not particularly limited, but high-purity is then unreasonable thinks.
In addition, boron sulfide, boron and sulphur also are not particularly limited, but high-purity is then unreasonable thinks.
In addition, with general formula Li
aMO
b[wherein, M represents to be selected from the element in phosphorus, silicon, aluminium, boron, sulphur, germanium, gallium, the indium, and a and b represent 1～10 number independently] compound of expression also is not particularly limited, but high-purity is then unreasonable thinks.
As with general formula Li
aMO
bThe compound of expression can be enumerated lithium metasilicate (Li ideally
4SiO
4), lithium borate (LiBO
2) and lithium phosphate (Li
3PO
4).
Described M is the compound of the compound of the element that is selected from phosphorus, aluminium, boron, germanium, gallium, indium beyond the silicon, needs only the compound of the formation crystal structure identical with lithium metasilicate, lithium borate and lithium phosphate, just is not particularly limited.
As these compounds, for example can enumerate LiAlO
2, Li
3BO
3, Li
2SO
4Deng.
Boron sulfide, boron, sulphur used among the present invention reach with general formula Li
aMO
bThe compound of expression is so long as high-purity then can be used commercially available product.
Among the present invention, in the raw mix with general formula Li
aMO
bThe content of the compound of expression is 0.5～30 mole of %, preferred 1～20 mole of %, more preferably 1～15 mole of %.
In addition, preferred 50～99 moles of % of the content of lithium sulfide, more preferably 55～85 moles of %, further preferred 60～80 moles of %, surplus in addition is the boron of boron sulfide or the mol ratio suitable with boron sulfide and the mixture of element sulphur.
The frit reaction temperature of described mixture is generally 400～1000 ℃, and preferred 600～1000 ℃, further preferred 700～1000 ℃, the frit reaction time is generally 0.1～12 hour, preferred 0.5～10 hour.
The chilling temperature of described frit reaction thing is generally below 10 ℃, and is preferred below 0 ℃, and its cooling rate is about 0.01～10000K/sec, preferred 1～10000K/sec.
The frit reaction thing that so obtains (sulfide-based glass) is glassy state (amorphous state fully), and as a rule, ionic conductance is 0.5～10 * 10
-4(S/cm).
Lithium-ion-conducting solid electrolyte of the present invention also can be by making described frit reaction thing (chalcogenide glass) heat treatment.
Heat treatment is 100～350 ℃, preferred 150～340 ℃, more preferably 180～330 ℃, though heat treatment time by heat treatment temperature about, be generally 0.01～240 hour, preferred 0.1～24 hour.
Utilize this heat treatment, can obtain the part or fully crystallization solid electrolyte.
The solid electrolyte that so obtains demonstrates 3.0 * 10 usually
-4～3.0 * 10
-3(S/cm) ionic conductance.
As the manufacture method of lithium sulfide used among the present invention,, just be not particularly limited so long as can reduce the method for impurity.
For example, also can make with extra care and obtain by the lithium sulfide that will utilize following method manufacturing.
In the middle of the following manufacture method, the method for preferred especially a or b.
Lithium hydroxide and hydrogen sulfide are reacted and generation hydrogen lithium sulfide, then with the method (Te Kaiping-No. 330312 communique) of this reactant liquor down 150～200 ℃ of following devulcanization hydrogenations at 0～150 ℃.
B. in non-proton organic solvent, make lithium hydroxide and hydrogen sulfide 150～200 ℃ of reactions down, directly generate the method (spy opens flat 7-330312 communique) of lithium sulfide.
The method (spy opens flat 9-283156 communique) that lithium hydroxide and gas shape sulphur source are reacted under 130～445 ℃ temperature.
Process for purification as the lithium sulfide that obtains as described above is not particularly limited.
As preferred method for refining, for example can enumerate and special be willing to 2003-363403 number etc.
Specifically, with the lithium sulfide that obtains as described above with an organic solvent, under the temperature more than 100 ℃, wash.
Under the temperature more than 100 ℃ with an organic solvent reason be because, because used organic solvent is that the temperature that the impurity N-methylamino butyric acid lithium (LMAB) that generates under the situation of N-N-methyl-2-2-pyrrolidone N-(NMP) dissolves in the organic solvent is 100 ℃ when lithium sulfide is made, therefore LMAB is dissolved in the organic solvent of washing usefulness, from lithium sulfide, removes.
The used preferred non-proton property polar solvent of organic solvent in the washing, in addition more preferably when lithium sulfide is made in used non-proton organic solvent and the washing used non-proton property polar organic solvent identical.
The non-proton property polar organic solvent that can use ideally as being in the suds, for example can enumerate the polar organic compound of non-proton property such as amide compound, lactam compound, urea compounds, organosulfur compound, ring type organic phosphorus compound, can be used as independent solvent or mixed solvent and use ideally.
In the middle of the polar organic solvent of these non-proton property,, for example can enumerate N, dinethylformamide, N, N-diethylformamide, N, N-dimethylacetylamide, N, N-Valpromide, N, N-dimethyl benzamide etc. as described amide compound.
In addition, as described lactam compound, for example can enumerate N-alkyl caprolactam classes such as caprolactam, N-methyl caprolactam, N-ethyl caprolactam, N-isopropyl caprolactam, N-isobutyl group caprolactam, N-n-pro-pyl caprolactam, N-normal-butyl caprolactam, N-cyclohexyl caprolactam; N-N-methyl-2-2-pyrrolidone N-(NMP), N-ethyl-2-pyrrolidone, N-isopropyl-2-Pyrrolidone, N-isobutyl group-2-Pyrrolidone, N-n-pro-pyl-2-Pyrrolidone, N-normal-butyl-2-Pyrrolidone, N-cyclohexyl-2-Pyrrolidone, N-methyl-3-N-methyl-2-2-pyrrolidone N-, N-ethyl-3-N-methyl-2-2-pyrrolidone N-, N-methyl-3,4,5-trimethyl-2-Pyrrolidone, N-methyl-2-piperidones, N-ethyl-2-piperidones, N-isopropyl-2-piperidones, N-methyl-6-methyl-2-piperidones, N-methyl-3-ethyl-2-piperidones etc.
As described organosulfur compound, for example can enumerate methyl-sulfoxide, diethyl sulfoxide, diphenylene sulfone (diphenylene sulfone), 1-methyl isophthalic acid-oxygen sulfone (oxosulfolane), 1-phenyl-1-oxygen sulfone etc.
Various non-proton property organic compounds can be used alone respectively, in addition also can be with two or more mixing, can also mix with other the solvent composition that does not hinder purpose of the present invention, and use as described non-proton organic solvent.
Preferred solvent is N-alkyl caprolactam and N-alkyl pyrrolidone in the described various non-proton organic solvent, and particularly preferred solvent is N-N-methyl-2-2-pyrrolidone N-(NMP).
The amount of used organic solvent is not particularly limited in the washing, and Xi Di number of times also is not particularly limited in addition, yet preferred more than 2 times.
Washing is preferably under the inert gases such as nitrogen, argon gas to be carried out.
Be in the suds under the temperature more than the boiling point of used non-proton organic solvent by the lithium sulfide that will be washed, under inert gas flows such as nitrogen, under normal pressure or decompression, dry more than 5 minutes, preferred about more than 2～3 hours, just can obtain high-purity lithium sulfide used among the present invention.
By using the solid electrolyte of the present invention that has excellent specific property as mentioned above, can obtain the all-solid lithium battery of long-time stability excellence.
As the negative electrode active material of all-solid lithium battery of the present invention, can enumerate carbon, indium, lithium, LiAl, LiWO
2, LiMoO
2, LiTiS
2Deng, preferred indium.
In addition, as positive active material, can enumerate LiCoO
2, LiNiO
2, LiMn
2O
4Etc. metal acid lithium salts and MnO
2, V
2O
5Deng, preferred LiCoO
2
The lithium-ion-conducting solid electrolyte that use utilizes method of the present invention to obtain is made the method for all-solid lithium battery can use known method in the past.
For example, in battery case, in the all-solid lithium battery that constitutes by hush panel, insulating packing, pole plate group, positive plate, positive wire, negative plate, negative wire, solid electrolyte, insulated ring, can with solid electrolyte with laminar shaping, pack into and use.
As the shape of all-solid lithium battery, no matter be any can use of large-scale shape used in Coin shape, coin shape, sheet type, cascade type, cylinder type, platypelloid type, square, the electric automobile etc. etc.
Embodiment
Below, will utilize embodiment and comparative example that the present invention is described in more detail, yet the present invention is not limited by these examples.
Reference example 1
(1) manufacturing of lithium sulfide
Lithium sulfide is to make according to the method that the spy opens first mode (2 operation method) of flat 7-330312 communique.
Specifically, in 10 liters of autoclaves that stirring vane is housed, add N-N-methyl-2-2-pyrrolidone N-(NMP) 3326.4g (33.6 moles) and lithium hydroxide 287.4g (12 moles), be warmed up to 130 ℃ with 300rpm.
After the intensification, in liquid, be blown into hydrogen sulfide 2 hours with 3 liters/minute feed speeds.
Next, with this reactant liquor (200cm under stream of nitrogen gas
3/ minute) heat up, with a part of devulcanization hydrogenation of the hydrogen sulfide that reacted.
Along with the carrying out of heating up, because of the water start vaporizer of the reaction by-product of described hydrogen sulfide and lithium hydroxide, and this water is discharged outside system by condenser condenses.
Water is distilled outside system remove in, the temperature of reactant liquor rises, yet stops to heat up in the moment that has arrived 180 ℃, remains uniform temperature.
The depriving hydrogen sulphide reaction finishes back (about 80 minutes), finishes reaction, has obtained lithium sulfide.
(2) lithium sulfide is refining
Behind the NMP decant in the slurry reaction solution of the 500mL that in described (1), obtains (NMP-lithium sulfide slip), add the NMP100mL dewatered, 105 ℃ of following stir abouts 1 hour.
Keeping under the state of this temperature the NMP decant.
Then, add NMP100mL,, under the state that keeps this temperature,, identical operations is carried out 4 times repeatedly totally the NMP decant 105 ℃ of following stir abouts 1 hour.
After decant finished, drying was 2 hours under decompression under 230 ℃, has obtained the high-purity lithium sulfide.
At high-purity lithium sulfide (Li with reference example 1
2S) 0.2903g (0.00632 mole), boron sulfide (B
2S
3) 0.3240g (0.00272 mole) and lithium metasilicate (Li
4SiO
4) after 0.0562g (0.00047 mole) mixed in mortar fully, granulating added and implemented to have carried out vacuum seal in the quartz glass tube that carbon applies.
Then, add in the vertical response stove, be warmed up to 800 ℃ with 4 hours, under this temperature, carried out frit reaction in 2 hours.
Reaction drops into chilling in the frozen water with quartz ampoule after finishing.
Quartz ampoule is opened, the powdered sample of the frit reaction thing (sulfide-based glass) of gained has been carried out X-ray diffraction, its result is that the peak of lithium sulfide, boron sulfide and lithium metasilicate disappears, and can confirm to have taken place vitrifying.
With this powdered sample 215 ℃ of following heat treatments 30 minutes.
Powdered sample to the heat treatment thing (sulfide-based sintered glass ceramics) of gained has carried out X-ray diffraction, and its result is to confirm to have taken place a part of crystallization (with reference to Fig. 1).
In addition, to the powdered sample of heat treatment thing, utilize AC impedence method to carry out the mensuration of conductivity, its result is that the ionic conductance under the room temperature is 10.1 * 10
-4S/cm.
Similarly, to the powdered sample of frit reaction thing (before the heat treatment), carried out X-ray diffraction (with reference to Fig. 1).
In addition, measured conductivity, its result is that the ionic conductance under the room temperature is 3.5 * 10
- 4S/cm.
The result of gained is shown in the table 1.And, in the table 1, before what is called is untreated and is meant heat treatment.
Except lithium metasilicate being replaced with 0.0336g (0.00028 mole), reaction and operation have been carried out in the same manner with embodiment 1.
The result of gained is shown in the table 1.
Except lithium metasilicate being replaced with 0.0456g (0.00038 mole), reaction and operation have been carried out in the same manner with embodiment 1.
The result of gained is shown in the table 1.
Except lithium metasilicate being replaced with 0.0692g (0.00058 mole), reaction and operation have been carried out in the same manner with embodiment 1.
The result of gained is shown in the table 1.
Embodiment 5
Except lithium metasilicate being replaced with 0.0815g (0.000688 mole), reaction and operation have been carried out in the same manner with embodiment 1.
The result of gained is shown in the table 1.And, before the what is called in the table 1 is untreated and is meant heat treatment.
Use heat treatment thing (sulfide-based glass ceramics) synthetic among the embodiment 1, sweep speed is made as 10mV/sec, in the scope of-0.5～10V, measured cyclic voltammetry curve.
The results are shown among Fig. 2.
And the longitudinal axis is represented electric current/A, and transverse axis is represented current potential (VvsLi
+/ Li).
Embodiment 7
Use heat treatment thing (sulfide-based glass ceramics) synthetic among the embodiment 4, as the cobalt acid lithium (LiCoO of positive active material
2), as the indium (In) of negative electrode active material, made lithium battery as followsly, estimated its battery behavior.
Use described negative electrode active material (56.6mg) and positive active material (11.9mg), folder is made 3 layers particle (pellet) shape every described heat treatment thing (165.5mg) between them, has formed the determination unit battery.
To this determination unit battery, the upper voltage limit that discharges and recharges is made as 3.7V, lower voltage limit is made as 2V, current density is made as 12.7 μ Acm
-2, studied and discharged and recharged.
The result of gained is shown among Fig. 3.
And the longitudinal axis is represented cell voltage/V, and transverse axis is represented the capacity/mAhg with respect to 1g cobalt acid lithium
-1
Comparative example 1
Except not adding lithium metasilicate, reaction and operation have been carried out in the same manner with embodiment 1.
The result of gained is shown in the table 1.
Comparative example 2
Except not adding lithium metasilicate, the high-purity lithium sulfide is made as 0.3489g (0.00759 mole), boron sulfide is made as 0.3396g (0.00288 mole) in addition, carried out reaction and operation in the same manner with embodiment 1.
The result of gained is shown in the table 1.
Comparative example 3
Except not adding lithium metasilicate, the high-purity lithium sulfide is made as 0.2651g (0.00577 mole), boron sulfide is made as 0.3349g (0.00284 mole) in addition, carried out reaction and operation in the same manner with embodiment 1.
The result of gained is shown in the table 1.
Table 1
At high-purity lithium sulfide (Li with reference example 1
2S) 0.2903g (0.00632 mole), boron sulfide (B
2S
3) 0.3204g (0.00272 mole) and lithium borate (LiBO
2) after 0.0338g (0.00068 mole) mixed in mortar fully, granulating added and implemented to have carried out vacuum seal in the quartz glass tube that carbon applies.
Then, add in the vertical response stove, be warmed up to 800 ℃ with 4 hours, under this temperature, carried out frit reaction in 2 hours.
Reaction drops into chilling in the frozen water with quartz ampoule after finishing.
Quartz ampoule is opened, the powdered sample of the frit reaction thing (sulfide-based glass) of gained has been carried out X-ray diffraction, its result is, do not observe the obvious diffraction line, can confirm that vitrifying has taken place sample.
Powdered sample to this frit reaction thing utilizes AC impedence method to measure conductivity, and its result is that the ionic conductance under the room temperature is 6.7 * 10
-4S/cm.
The result of gained is shown in the table 2.And, in the table 2, before what is called is untreated and is meant heat treatment.
Embodiment 9
Except lithium borate being replaced with 0.0443g (0.00089 mole), reaction and operation have been carried out in the same manner with embodiment 8.
Powdered sample to the frit reaction thing (sulfide-based glass) of gained has carried out X-ray diffraction, and its result is, does not observe the obvious diffraction line, can confirm that vitrifying has taken place sample.
Powdered sample to this frit reaction thing has been measured conductivity, and its result is that the ionic conductance under the room temperature is 9.5 * 10
-4S/cm.
The result of gained is shown in the table 2.
Except lithium borate being replaced with lithium phosphate (Li
3PO
4), use amount is replaced with 0.0534g (0.000475 mole) in addition, carried out reaction and operation in the same manner with embodiment 8.
Frit reaction thing (sulfide-based glass to gained; Before the heat treatment) powdered sample carried out X-ray diffraction, its result is, do not observe the obvious diffraction line, can confirm that vitrifying has taken place sample.
Powdered sample to this frit reaction thing has been measured conductivity, and its result is that the ionic conductance under the room temperature is 8.1 * 10
-4S/cm.
With the powdered sample of this frit reaction thing (before the heat treatment) 230 ℃ of following heat treatments 30 minutes.
Powdered sample to the heat treatment thing (sulfide-based sintered glass ceramics) of gained has been measured conductivity, and its result is that the ionic conductance under the room temperature is 22.0 * 10
-4S/cm.
The result of gained is shown in the table 2.
Embodiment 11
Except lithium borate being replaced with lithium phosphate (Li
3PO
4), use amount is replaced with 0.0787g (0.00068 mole) in addition, carried out reaction and operation in the same manner with embodiment 8.
Frit reaction thing (sulfide-based glass to gained; Before the heat treatment) powdered sample carried out X-ray diffraction, its result is, do not observe the obvious diffraction line, can confirm that vitrifying has taken place sample.
Powdered sample to this frit reaction thing has been measured conductivity, and its result is that the ionic conductance under the room temperature is 8.0 * 10
-4S/cm.
With the powdered sample of this frit reaction thing (before the heat treatment) 230 ℃ of following heat treatments 30 minutes.
Powdered sample to the heat treatment thing (sulfide-based glass ceramics) of gained has been measured conductivity, and its result is that the ionic conductance under the room temperature is 24.0 * 10
-4S/cm.
The result of gained is shown in the table 2.
Except lithium borate being replaced with lithium phosphate (Li
3PO
4), use amount is replaced with 0.0324g (0.00028 mole) in addition, carried out reaction and operation in the same manner with embodiment 8.
Frit reaction thing (sulfide-based glass to gained; Before the heat treatment) powdered sample carried out X-ray diffraction, its result is, do not observe the obvious diffraction line, can confirm that vitrifying has taken place sample.
Powdered sample to this frit reaction thing has been measured conductivity, and its result is that the ionic conductance under the room temperature is 6.1 * 10
-4S/cm.
With the powdered sample of this frit reaction thing (before the heat treatment) 230 ℃ of following heat treatments 30 minutes.
Powdered sample to the heat treatment thing (sulfide-based glass ceramics) of gained has been measured conductivity, and its result is that the ionic conductance under the room temperature is 19.0 * 10
-4S/cm.
The result of gained is shown in the table 2.And, before the what is called in the table 2 is untreated and is meant heat treatment.
Table 2
The industrial possibility of utilizing
The lithium-ion-conducting solid electrolyte that utilizes method of the present invention to obtain can be used as and carries letter The breath terminal, carry e-machine, household small-size electrical storage device, two taking turns and rub take motor as power source The all-solid lithium battery of motorcycle, electric automobile, compound electric automobile etc. uses, yet not special Be defined in them.
Claims (8)
1. lithium-ion-conducting solid electrolyte, it is to contain 60～80 moles of % lithium sulfide (Li
2S), 1～15 mole of % is with Li
aMO
bCompound, the surplus of expression are boron sulfide (B
2S
3) raw mix frit reaction thing chilling and sulfide-based glass; The sulfide-based sintered glass ceramics that this sulfide-based glass heat processing is got; Or the mixture of the ratio arbitrarily of above-mentioned sulfide-based glass and above-mentioned sulfide-based sintered glass ceramics,
Wherein, M represents to be selected from the element in phosphorus (P), silicon (Si), aluminium (Al), boron (B), sulphur (S), germanium (Ge), gallium (Ga), the indium (In), and a and b represent 1～10 number independently.
2. a lithium-ion-conducting solid electrolyte is characterized in that, has lithium sulfide (Li
2S): with Li
aMO
bThe mole % ratio of the compound of expression be 60～80: 1～15 and surplus be boron sulfide (B
2S
3) composition.
Wherein, M represents to be selected from the element in phosphorus (P), silicon (Si), aluminium (Al), boron (B), sulphur (S), germanium (Ge), gallium (Ga), the indium (In), and a and b represent 1～10 number independently.
3. a method for producing lithium ion conductive solid electrolyte is characterized in that, will have lithium sulfide (Li2S): with Li
aMO
bThe mole % ratio of the compound of expression be 60～80: 1～15 and surplus be boron sulfide (B
2S
3) the sulfide-based glass of composition under 100～350 ℃, heat-treat.
Wherein, M represents to be selected from the element in phosphorus (P), silicon (Si), aluminium (Al), boron (B), sulphur (S), germanium (Ge), gallium (Ga), the indium (In), and a and b represent 1～10 number independently.
According in the claim 3 record method for producing lithium ion conductive solid electrolyte, wherein, with general formula Li
aMO
bThe compound of expression is selected from lithium metasilicate, lithium borate, lithium phosphate.
5. according to the method for producing lithium ion conductive solid electrolyte of claim 3 or 4 records, wherein, replace boron sulfide, and use the boron of suitable mol ratio and the mixture of element sulphur.
6. one kind is utilized any lithium-ion-conducting solid electrolyte that the manufacture method of being put down in writing obtains in the claim 3～5.
7. secondary lithium batteries solid electrolyte that uses claim 1,2 or 6 lithium-ion-conducting solid electrolytes of being put down in writing to form.
8. all-solid lithium battery that the secondary lithium batteries solid electrolyte that uses in the claim 7 record forms.
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| JP2010225522A (en) * | 2009-03-25 | 2010-10-07 | Sony Corp | Electrolyte, and secondary battery |
| US20110171528A1 (en) * | 2010-01-12 | 2011-07-14 | Oladeji Isaiah O | Solid state electrolytes having high lithium ion conduction |
| JP5561383B2 (en) * | 2013-01-11 | 2014-07-30 | トヨタ自動車株式会社 | Sulfide solid electrolyte material, battery, and method for producing sulfide solid electrolyte material |
| WO2018181674A1 (en) * | 2017-03-30 | 2018-10-04 | Tdk株式会社 | All-solid secondary battery |
| EP3951981A4 (en) * | 2019-03-26 | 2022-11-23 | NGK Insulators, Ltd. | All-solid-state secondary battery |
| CN112242555B (en) * | 2019-07-16 | 2021-10-22 | 宁德时代新能源科技股份有限公司 | Sulfide solid electrolyte sheet and preparation method thereof |
| US20230047398A1 (en) * | 2019-12-27 | 2023-02-16 | Microvast Power Systems Co.,Ltd. | Electrolyte containing solid particles and lithium ion secondary battery |
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| JP2002109955A (en) * | 2000-10-02 | 2002-04-12 | Osaka Prefecture | Sulfide crystallized glass, solid electrolyte, and fully solid secondary cell |
| US20030205467A1 (en) * | 1995-11-15 | 2003-11-06 | Jie Fu | Alkali ion conductive glass-ceramics and electric cells and gas sensors using the same |
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| US20030205467A1 (en) * | 1995-11-15 | 2003-11-06 | Jie Fu | Alkali ion conductive glass-ceramics and electric cells and gas sensors using the same |
| US6200707B1 (en) * | 1997-09-03 | 2001-03-13 | Matsushita Electric Industrial Co., Ltd. | Solid electrolytic moldings, electrode moldings, and electrochemical elements including a polybutadiene block copolymer |
| JP2002109955A (en) * | 2000-10-02 | 2002-04-12 | Osaka Prefecture | Sulfide crystallized glass, solid electrolyte, and fully solid secondary cell |
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| CN109065837A (en) * | 2014-11-10 | 2018-12-21 | 株式会社村田制作所 | lithium ion conductor, battery and electronic device |
| CN109065837B (en) * | 2014-11-10 | 2021-08-24 | 株式会社村田制作所 | Lithium ion conductor, battery, and electronic device |
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