CN103560267A - Electrolyte material for all solid-state lithium secondary battery, preparation method for electrolyte material and all solid-state lithium secondary battery - Google Patents
Electrolyte material for all solid-state lithium secondary battery, preparation method for electrolyte material and all solid-state lithium secondary battery Download PDFInfo
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- CN103560267A CN103560267A CN201310534862.8A CN201310534862A CN103560267A CN 103560267 A CN103560267 A CN 103560267A CN 201310534862 A CN201310534862 A CN 201310534862A CN 103560267 A CN103560267 A CN 103560267A
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- secondary battery
- lithium secondary
- solid lithium
- battery electrolyte
- solid
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 210
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002001 electrolyte material Substances 0.000 title abstract 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims description 151
- 239000003792 electrolyte Substances 0.000 claims description 143
- 239000000956 alloy Substances 0.000 claims description 32
- 229910045601 alloy Inorganic materials 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000000227 grinding Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 13
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 13
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- VIEXQFHKRAHTQS-UHFFFAOYSA-N chloroselanyl selenohypochlorite Chemical compound Cl[Se][Se]Cl VIEXQFHKRAHTQS-UHFFFAOYSA-N 0.000 claims description 7
- 238000000713 high-energy ball milling Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- -1 phosphorus nitride Chemical class 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- 229910052810 boron oxide Inorganic materials 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- TXLQIRALKZAWHN-UHFFFAOYSA-N dilithium carbanide Chemical compound [Li+].[Li+].[CH3-].[CH3-] TXLQIRALKZAWHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- PEXNRZDEKZDXPZ-UHFFFAOYSA-N lithium selenidolithium Chemical compound [Li][Se][Li] PEXNRZDEKZDXPZ-UHFFFAOYSA-N 0.000 claims description 3
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims 1
- 229910052755 nonmetal Inorganic materials 0.000 abstract 3
- 239000002019 doping agent Substances 0.000 abstract 2
- 229910001216 Li2S Inorganic materials 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 57
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 32
- 229910001416 lithium ion Inorganic materials 0.000 description 32
- 238000000034 method Methods 0.000 description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 239000007784 solid electrolyte Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 13
- 238000007789 sealing Methods 0.000 description 13
- 238000000498 ball milling Methods 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 238000009413 insulation Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- 102000004310 Ion Channels Human genes 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 229910003480 inorganic solid Inorganic materials 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000000970 chrono-amperometry Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- COOGPNLGKIHLSK-UHFFFAOYSA-N aluminium sulfide Chemical compound [Al+3].[Al+3].[S-2].[S-2].[S-2] COOGPNLGKIHLSK-UHFFFAOYSA-N 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
- 238000000748 compression moulding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002241 glass-ceramic Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910000952 Be alloy Inorganic materials 0.000 description 1
- 206010058490 Hyperoxia Diseases 0.000 description 1
- 229910018092 Li 2 S-Al 2 S 3 Inorganic materials 0.000 description 1
- 229910020346 SiS 2 Inorganic materials 0.000 description 1
- GHJIICAEBSDGDU-UHFFFAOYSA-N [S].[Si].[La].[Li] Chemical compound [S].[Si].[La].[Li] GHJIICAEBSDGDU-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000000222 hyperoxic effect Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The invention provides an electrolyte material (LiaPbScMd) for an all solid-state lithium secondary battery and a preparation method for the electrolyte material. The electrolyte material, shown in a formula (I) LiaPbScMd, for the all solid-state lithium secondary battery is prepared from Li2S, P2S5 and a dopant, wherein the dopant is selected from one or more of compounds of nonmetal elements in main groups III, IV, V, VI and VII of lithium and compounds formed from at least two of the nonmetal elements in the main groups III, IV, V, VI and VII; in the formula (I), M is selected from one or more of the nonmetal elements in the main groups III, IV, V, VI and VII, a is more than 0 and less than or equal to 10, b is more than 0 and less than or equal to 5, c is more than 0 and less than or equal to 15, and d is more than 0 and less than 1. The electrolyte material for the all solid-state lithium secondary battery has high electrical conductivity, high electrochemical stability and the like, and is favorable for application. The invention also provides the all solid-state lithium secondary battery.
Description
Technical field
The present invention relates to lithium secondary battery technical field, particularly a kind of all solid lithium secondary battery electrolyte, its preparation method and all solid lithium secondary battery.
Background technology
Because lithium secondary battery has that power output is large, energy density is high, long service life, average output voltage is high, self discharge is little, memory-less effect, can fast charging and discharging, cycle performance is superior and the plurality of advantages such as non-environmental-pollution, the first choice that it has become the current rechargable power supplies for portable type electronic product, is also considered to the most competitive Vehicular dynamic battery.Therefore, current, lithium secondary battery has been come into huge numbers of families, becomes social inalienable part.In general, lithium secondary battery mainly comprises liquid lithium secondary cell and solid lithium secondary cell.In solid lithium secondary cell, containing liquid electrolyte, do not adopt the battery of solid electrolyte material to be called all solid lithium secondary battery.Because all solid lithium secondary battery has the incomparable fail safe of liquid lithium secondary cell, and be expected to thoroughly eliminate the potential safety hazard existing in battery use procedure, it more meets the demand of electric automobile and scale energy storage field future development.
The core component of all solid lithium secondary battery comprises solid electrolyte material, and its performance quality is the key point that can all solid lithium secondary battery realize high performance.Solid electrolyte material mainly contains two large classes: organic polymer electrolyte and inorganic solid electrolyte material.In inorganic solid electrolyte material, because the electronegativity of sulphur is less, to the binding force of lithium ion is weak and its radius is larger, ion channel is larger, be conducive to the migration of lithium ion, make sulfide-based electrolyte demonstrate higher lithium ion conductivity, become inorganic solid electrolyte material with fastest developing speed at present.Prior art discloses multiple sulfide-based electrolyte, and if Granted publication is number for the Chinese patent literature of CN100486025C discloses a kind of solid electrolyte material for serondary lithium battery, this solid electrolyte material is Li
2s-Al
2s
3, i.e. LiAlS
2, wherein the atomic molar of Li, Al and S ratio is 1:1:2, and LiAlS
2for non-crystalline material, it take aluminium sulfide as skeleton, and lithium ion is diffused in the skeleton of aluminium sulfide, but the lithium ion conductivity of this solid electrolyte material is at room temperature only about 1.77 * 10
-5scm
-1, cause the conductivity of this solid electrolyte material poor.
In order further to improve the lithium ion conductivity of sulfide-based electrolyte, Granted publication is number for the Chinese patent literature of CN100486024C discloses a kind of lithium-lanthanum-silicon-sulfur solid electrolyte material for serondary lithium battery, and this solid electrolyte material is Li
2s, La
2s
3and SiS
2three kinds of different sulfide are composited according to the mol ratio of 6:0.5:3, and its lithium ion conductivity is at room temperature about 5.35 * 10
-5scm
-1.But the lithium ion conductivity of above-mentioned solid electrolyte material is at room temperature still not high, its conductivity needs further to be improved.
Summary of the invention
In order to solve above technical problem, the invention provides a kind of all solid lithium secondary battery electrolyte, its preparation method and all solid lithium secondary battery, all solid lithium secondary battery electrolyte provided by the invention at room temperature has good conductivity, is convenient to application.
The invention provides all solid lithium secondary battery electrolyte shown in a kind of formula (I):
Li
aP
bS
cM
d（I）；
In formula (I), M is one or more in III, IV, V, VI and VII main group nonmetalloid; 0 < a≤10,0 < b≤5,0 < c≤15,0 < d < 1.
Preferably, M is one or more in boron element, carbon, nitrogen element, oxygen element, selenium element, chlorine element, bromo element and I.
The preparation method who the invention provides a kind of all solid lithium secondary battery electrolyte, comprising:
By Li
2s, P
2s
5after mixing with alloy, grind, the time of described grinding is 5h at least, obtains all solid lithium secondary battery electrolyte;
Described alloy is III, IV, V, VI and the VII main group nonmetalloid compound of lithium, and one or more in the compound that at least two elements form in III, IV, V, VI and VII main group nonmetalloid.
Preferably, described alloy is one or more in lithium chloride, lithium bromide, lithium iodide, boronation lithium, lithium carbide, lithium nitride, lithia, lithium selenide, phosphorus nitride, selenium chloride, boron oxide and phosphorous oxide.
Preferably, described Li
2s, P
2s
5with the mol ratio of alloy be 1:(0.01～1): (0.001～0.1).
Preferably, described in be ground to high-energy ball milling, rotating speed is 200rpm～600rpm, the time is 6h～60h, ratio of grinding media to material is 1:1～60:1.
Preferably, by Li
2s, P
2s
5after grinding with the mixture of alloy, also comprise:
Mixture after grinding is heat-treated, and described heat treated temperature is 100 ℃～500 ℃, obtains all solid lithium secondary battery electrolyte.
Preferably, described grinding is carried out under inert atmosphere, and the water content of described inert atmosphere is less than 100ppm, and oxygen content is less than 100ppm.
The present invention also provides a kind of all solid lithium secondary battery, comprises positive pole, negative pole and all solid lithium secondary battery electrolyte, and wherein, described all solid lithium secondary battery electrolyte is described all solid lithium secondary battery electrolyte.
Compared with prior art, the preparation method of all solid lithium secondary battery electrolyte provided by the invention is first by Li
2s, P
2s
5mix with alloy, then grind at least 5h, obtain all solid lithium secondary battery electrolyte; Described alloy is III, IV, V, VI and the VII main group nonmetalloid compound of lithium, and one or more in the compound that at least two elements form in III, IV, V, VI and VII main group nonmetalloid.In the present invention, described Li
2s and P
2s
5by grinding, first form amorphous powder, then form electrolyte system.When forming electrolyte system, amorphous powder is softening, causes in system intercrystalline contact tightr, reduced grain boundary resistance, make lithium ion conductivity not be subject to the impact of grain boundary effect, almost identical with system conductivity, thus guaranteed lithium ion conductivity.Simultaneously, the present invention is by the doping of described alloy, make described all solid lithium secondary battery electrolyte there is formula (I) atomic ratio, in system, introduce III, IV, V, VI and VII main group nonmetalloid, thereby in system, produce space or widen the ion channel of system, and the system of reduction skeleton and the interionic active force of migration, not only the lithium ion conductivity of all solid lithium secondary battery electrolyte can be further improved, and its electrochemical stability can be improved.Experiment shows, the lithium ion conductivity of all solid lithium secondary battery electrolyte provided by the invention is at room temperature up to～10
-3scm
-1, conductivity is better, and it has the electrochemical window higher than 10V, and electrochemical stability is better, is beneficial to application.
In addition, the preparation method of all solid lithium secondary battery electrolyte provided by the invention is easy, easy operating, safe and reliable, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the electrolyte of embodiment 1 preparation;
Fig. 2 is the AC impedance spectrogram of all solid lithium secondary battery electrolyte of embodiment 1 preparation;
Fig. 3 is the lithium ion conductivity of all solid lithium secondary battery electrolyte and the temperature variant curve chart of logarithm of temperature product of embodiment 1 preparation;
Fig. 4 is the curve chart that the conductivity at room temperature of all solid lithium secondary battery electrolyte of embodiment 1 preparation changed with the air exposure time;
Fig. 5 is the cyclic voltammetry curve figure of all solid lithium secondary battery electrolyte/lithium metal experiment half-cell of embodiment 1 preparation;
Fig. 6 is the chronoamperometry test result figure of all solid lithium secondary battery electrolyte of embodiment 1 preparation;
The first charge-discharge figure of all solid lithium secondary battery that Fig. 7 provides for embodiment 1.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The invention provides all solid lithium secondary battery electrolyte shown in a kind of formula (I):
Li
aP
bS
cM
d（I）；
In formula (I), M is one or more in III, IV, V, VI and VII main group nonmetalloid; 0 < a≤10,0 < b≤5,0 < c≤15,0 < d < 1.
All solid lithium secondary battery electrolyte provided by the invention is glass ceramics solid electrolyte material, at room temperature has higher lithium ion conductivity, excellent conductivity.
Described all solid lithium secondary battery electrolyte has formula (I) atomic ratio, wherein, Li is elemental lithium, P is P elements, S is element sulphur, described all solid lithium secondary battery electrolyte belongs to binary sulfide class electrolyte, because the electronegativity of sulphur is less, to the binding force of lithium ion is weak and radius is larger, ion channel is larger, be conducive to the migration of lithium ion, thereby make sulfide-based electrolyte demonstrate higher lithium ion conductivity, and become inorganic solid electrolyte material with fastest developing speed at present;
M is one or more in III, IV, V, VI and VII main group nonmetalloid, can in electrolyte system, produce space or widen the ion channel of system, and the system of reduction skeleton and the interionic active force of migration, not only the lithium ion conductivity of all solid lithium secondary battery electrolyte can be further improved, and its electrochemical stability can be improved.Described M is preferably one or more in boron element, carbon, nitrogen element, oxygen element, selenium element, chlorine element, bromo element and I, more preferably boron element, carbon, nitrogen element, selenium element, chlorine element, bromo element or I, be beneficial to application.When described M is two or more element, the present invention is not particularly limited the ratio of these two kinds of elements, and its summation can function as described above in limited range.
0 < a≤10, preferably 1 < a≤8, more preferably 1.2 < a≤5, most preferably 1.3 < a≤3; 0 < b≤5, preferably 0.1 < b≤3, more preferably 0.5 < b≤2; 0 < c≤15, preferably 1 < c≤10, more preferably 2 < c≤6; 0 < d < 1, preferably 0.01≤d < 0.5.
The present invention is not particularly limited the preparation method of described all solid lithium secondary battery electrolyte, and it can adopt following methods to make.
The preparation method who the invention provides a kind of all solid lithium secondary battery electrolyte, comprising:
By Li
2s, P
2s
5after mixing with alloy, grind, the time of described grinding is 5h at least, obtains all solid lithium secondary battery electrolyte;
Described alloy is III, IV, V, VI and the VII main group nonmetalloid compound of lithium, and one or more in the compound that at least two elements form in III, IV, V, VI and VII main group nonmetalloid.
Method provided by the invention is with Li
2s, P
2s
5with alloy be raw material, prepare all solid lithium secondary battery electrolyte, it belongs to binary sulfide electrolyte, at room temperature lithium ion conductivity is higher, has good conductivity.
In the present invention, described Li
2s and P
2s
5after mixing, by grinding, can form the system of glass ceramics, the composite material that glassy phase combines with crystalline phase.
Described alloy is the III of lithium, IV, V, VI and VII main group nonmetalloid compound are (as the halide of lithium, oxide and nitride etc.), and by III, IV, V, in VI and VII main group nonmetalloid, the compound of at least two element formation is (as phosphorous oxide, selenium chloride and phosphorus nitride etc.) in one or more, namely can to adopt the halide of lithium be alloy to the embodiment of the present invention, can adopt selenium chloride is alloy, also can adopt the oxide of lithium and the nitride of lithium is alloy, also can adopt phosphorous oxide and boron oxide is alloy, can also adopt halide and the selenium chloride of lithium is alloy, can also adopt the oxide of lithium, the nitride of lithium and phosphorus nitride are alloy, etc. multiple combination.The present invention is by the grinding described alloy that adulterates, in above-mentioned system, introduce one or more in III, IV, V, VI and VII main group nonmetalloid, in system, produce space or widen the ion channel of system, and the system of reduction skeleton and the interionic active force of migration, not only the lithium ion conductivity of all solid lithium secondary battery electrolyte can be further improved, and its electrochemical stability can be improved.
Wherein, described alloy is preferably lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (LiI), boronation lithium, lithium carbide (Li
2c
2), lithium nitride (Li
3n), lithia, lithium selenide, phosphorus nitride, selenium chloride, boron oxide and phosphorous oxide (P
2o
5) in one or more, more preferably lithium chloride, lithium bromide, lithium iodide, lithium carbide, lithium nitride, selenium chloride (SeCl
4), boron oxide (B
2o
3) or phosphorous oxide.
The present invention is not particularly limited the quality of described alloy, and the quality optimization of described alloy is Li
2s and P
2s
5gross mass 0.1%～10%, more preferably 0.5%～5%, most preferably be 1%～3%.
The present invention is to described Li
2s, P
2s
5be not particularly limited described Li with the mol ratio of alloy
2s, P
2s
5be preferably 1:(0.01～1 with the mol ratio of alloy): (0.001～0.1), more preferably 1:(0.05～0.5): (0.005～0.05), most preferably is 1:(0.1～0.3): (0.01～0.03).When described alloy is two or more compound, the present invention is not particularly limited the ratio of these two kinds of compounds, and its summation can function as described above in limited range.
The embodiment of the present invention is preferably mixed above-mentioned raw materials under inert atmosphere, then grinds the regular hour, obtains all solid lithium secondary battery electrolyte.
Described mixing and grinding are preferably carried out under inert atmosphere, are beneficial to raising product purity.The present invention is not particularly limited described mixing, and raw material is mixed.Described inert atmosphere is as nitrogen or argon gas etc., and water content is preferably less than 100ppm, and oxygen content is preferably less than 100ppm.
The time of described grinding is 5h at least, to obtain all solid lithium secondary battery electrolyte.The number of times of described grinding can be once or twice more than; Described grinding comprises the mechanical lappings such as ball milling, high-energy ball milling, barreling and vibration milling, is preferably high-energy ball milling, has efficiency compared with advantages of higher.The rotating speed of described high-energy ball milling is preferably 200rpm～600rpm, more preferably 300rpm～500rpm; The time of described high-energy ball milling is preferably 6h～60h, more preferably 10h～50h; The ratio of grinding media to material of described high-energy ball milling is preferably 1:1～60:1, more preferably 1:5～50:1.
By Li
2s, P
2s
5after grinding with the mixture of alloy, the embodiment of the present invention preferably also comprises:
Mixture after grinding is just expected to heat-treat, and described heat treated temperature is 100 ℃～500 ℃, obtains all solid lithium secondary battery electrolyte.
The embodiment of the present invention is taken out just material, is ground after even and carries out compressing tablet, obtains sheet and just expects; Then by described sheet just material pack in quartz glass tube, heat-treat after vacuumizing and use oxyhydrogen flame sealing by fusing.Described heat treatment is sintering namely, and obtaining sintered body is electrolyte.
In the present invention, the pressure of described compressing tablet can be 10MPa;
The described vacuum degree vacuumizing is preferably less than 100Pa;
Described heat treated temperature is preferably 150 ℃～400 ℃, more preferably 200 ℃～300 ℃;
Described heat treated number of times can be for more than once or twice;
Described heat treatment can be specially:
The quartz glass tube that mixed raw material is housed is preferably heated with the heating rate of 2 ℃/min; preferably 0.1h～30h, more preferably 0.5h～20h, most preferably after 1h～15h, carry out water-cooled quenching or cool to room temperature with the furnace; then open pipe grinding evenly under argon gas atmosphere protection under the condition that is preferably 0.1ppm in water content, obtains all solid lithium secondary battery electrolyte.
Obtain after all solid lithium secondary battery electrolyte, the present invention carries out XRD test to it.Test result demonstration, described all solid lithium secondary battery electrolyte has formula (I) atomic ratio.In other words, the described all solid lithium secondary battery electrolyte described Li that serves as reasons
2s, P
2s
5with the electrolyte system that alloy forms, can also say the Li of described alloy doping
2s-P
2s
5system.
And the present invention tests the chemical property of described all solid lithium secondary battery electrolyte and air-stable performance.Test result demonstration, the lithium ion conductivity of gained all solid lithium secondary battery electrolyte is at room temperature up to～10
-3scm
-1, also there is the electrochemical window higher than 10V.Show that all solid lithium secondary battery electrolyte provided by the invention at room temperature has good conductivity, electrochemical stability and air stability, cost is lower, is beneficial to application.
In addition, the preparation method of all solid lithium secondary battery electrolyte provided by the invention is easy, easy operating, is applicable to suitability for industrialized production.
The present invention also provides a kind of all solid lithium secondary battery, comprises positive pole, negative pole and all solid lithium secondary battery electrolyte, and wherein, described all solid lithium secondary battery electrolyte is all solid lithium secondary battery electrolyte mentioned above.
In the present invention, above-mentioned all solid lithium secondary battery electrolyte can make described all solid lithium secondary battery have the application performances such as good conductivity, electrochemical stability and air stability.
The present invention is not particularly limited described positive pole, and described positive pole can be made by compounds such as cobalt acid lithium or LiMn2O4s; The present invention is not particularly limited described negative pole, and described negative pole can adopt graphite etc. to make.
In order further to understand the present invention, below in conjunction with embodiment, all solid lithium secondary battery electrolyte provided by the invention, its preparation method and all solid lithium secondary battery are described in detail.
According to mol ratio, be 1:0.4:0.01, weigh purity and be respectively more than 99% Li
2s, P
2s
5with Li
3n; Under argon gas atmosphere protection, in water content, be less than after above-mentioned raw materials being mixed under the condition of 100ppm and grind, then adopt high energy ball mill ball milling 40h, obtain just material;
Take out described just material, after being ground evenly, adopt the pressure of 10MPa to carry out compressing tablet, then the sheet obtaining is just expected to pack in quartz glass tube, be evacuated to after vacuum degree is less than 100Pa and use oxyhydrogen flame sealing by fusing, again the quartz glass tube that said mixture is housed is heated to 270 ℃ with the heating rate of 2 ℃/min, insulation 4h, cool to the furnace after room temperature, under the condition that is 100ppm in water content, open pipe also grinds evenly again, again pack in quartz glass tube subsequently, be evacuated to after vacuum degree is less than 100Pa and use oxyhydrogen flame sealing by fusing, heating rate with 2 ℃/min is heated to 260 ℃, insulation 2h, after cooling to room temperature with the furnace, grind evenly, obtain all solid lithium secondary battery electrolyte, be Li
3the Li of N doping
2s-P
2s
5system (70%Li
2s-29%P
2s
5-1%Li
3n).
Obtain, after all solid lithium secondary battery electrolyte, it being carried out to XRD test.As shown in Figure 1, Fig. 1 is the XRD figure of the electrolyte of embodiment 1 preparation to test result.As can be seen from Figure 1 there is being similar to Li in gained electrolyte, near 30 ℃
7p
3s
11the principal crystalline phase diffraction maximum of fast-ionic conductor, shows that gained electrolyte is Li
1.43p
0.58s
2.15n
0.01.
And, described all solid lithium secondary battery electrolyte is carried out to chemical property and the test of air-stable performance.
Under the condition that is 100ppm in water content by described all solid lithium secondary battery electrolyte, being pressed into diameter is that 10mm, thickness are the compressing tablet that 1.5mm, pressure position are 10MPa, take gold electrode as blocking electrode, at room temperature carry out EIS test, to characterize its electric conductivity.Result as shown in Figures 2 and 3, Fig. 2 is the AC impedance spectrogram of all solid lithium secondary battery electrolyte of embodiment 1 preparation, and Fig. 3 is the lithium ion conductivity of all solid lithium secondary battery electrolyte and the temperature variant curve chart of logarithm of temperature product of embodiment 1 preparation.As can be seen from Figures 2 and 3, body series has ionic conduction characteristic, and under the condition of 25 ℃, lithium ion conductivity is 1.99 * 10
-3scm
-1, show that gained all solid lithium secondary battery electrolyte at room temperature has good conductivity.
Described all solid lithium secondary battery electrolyte is at room temperature exposed to certain hour in air, tests its ionic conductivity.Test result is referring to Fig. 4, and Fig. 4 is the curve chart that the conductivity at room temperature of all solid lithium secondary battery electrolyte of embodiment 1 preparation changed with the air exposure time.As can be seen from Figure 4, along with the prolongation of open-assembly time, the ionic conductivity of electrolyte reduces gradually, but after exposing 25h, its conductivity at room temperature is still higher, shows that the air stability of gained electrolyte is better.
By after above-mentioned all solid lithium secondary battery electrolyte compression molding, take gold electrode as to electrode, take lithium metal as reference electrode, under the condition that is 100ppm in water content, be assembled into experiment half-cell, between 0～10V, in room temperature, carry out cyclic voltammetry, to characterize the decomposition voltage of the relative lithium metal of gained all solid lithium secondary battery electrolyte.As shown in Figure 5, Fig. 5 is the cyclic voltammetry curve figure of all solid lithium secondary battery electrolyte/lithium metal experiment half-cell of embodiment 1 preparation to test result.As shown in Figure 5, described all solid lithium secondary battery electrolyte has the electrochemical window higher than 10V, shows that the electrochemical stability of all solid lithium secondary battery electrolyte that the present embodiment provides is better.
By after above-mentioned all solid lithium secondary battery electrolyte compression molding, take lithium electrode and gold electrode respectively as work electrode, under the condition that is 100ppm in water content, be assembled into lithium electrode/solid electrolyte/lithium electrode, gold electrode/solid electrolyte/gold electrode test system, at 1V, apply under voltage and carry out chronoamperometry test in room temperature, to characterize the electronic conductance of gained all solid lithium secondary battery electrolyte and the ratio of ionic conductance.As shown in Figure 6, Fig. 6 is the chronoamperometry test result figure of all solid lithium secondary battery electrolyte of embodiment 1 preparation to test result.As shown in Figure 6, described all solid lithium secondary battery electrolyte has good ionic conductance and good electronic isolation, shows that all solid lithium secondary battery electrolyte that the present embodiment provides can be used as the barrier film use in battery.
Adopt cobalt acid lithium to be made as positive pole, adopt graphite-made as negative pole, make and obtain all solid lithium secondary battery together with above-mentioned all solid lithium secondary battery electrolyte, and carry out charge-discharge test, first charge-discharge figure during its 0.5C sees Fig. 7, the first charge-discharge figure of all solid lithium secondary battery that Fig. 7 provides for embodiment 1.From electrochemical property test result and Fig. 7 of above-mentioned all solid lithium secondary battery electrolyte, gained all solid lithium secondary battery has good conductivity and electrochemical stability.
Embodiment 2
According to mol ratio, be 1:0.4:0.01, weigh purity and be respectively more than 99% Li
2s, P
2s
5with LiI; Under argon gas atmosphere protection, in water content, be less than after above-mentioned raw materials being mixed under the condition of 100ppm and grind, then adopt high energy ball mill ball milling 40h, obtain just material;
Take out described just material, after being ground evenly, adopt the pressure of 10MPa to carry out compressing tablet, then the sheet obtaining is just expected to pack in quartz glass tube, be evacuated to after vacuum degree is less than 100Pa and use oxyhydrogen flame sealing by fusing, again the quartz glass tube that said mixture is housed is heated to 250 ℃ with the heating rate of 2 ℃/min, insulation 2h, cool to the furnace after room temperature, under the condition that is 0.1ppm in water content, open pipe also grinds evenly again, obtain all solid lithium secondary battery electrolyte, i.e. the Li of LiI doping
2s-P
2s
5system (70%Li
2s-29%P
2s
5-1%LiI).
Obtain, after all solid lithium secondary battery electrolyte, according to the method for embodiment 1, it being carried out to XRD test.Test result shows, gained electrolyte is Li
1.41p
0.58s
2.15i
0.01.
And, according to the method for embodiment 1, described all solid lithium secondary battery electrolyte is carried out to chemical property and the test of air-stable performance.Test result demonstration, under the condition of 25 ℃, its lithium ion conductivity is 3.1 * 10
-3scm
-1, and there is the electrochemical window higher than 10V, show that all solid lithium secondary battery electrolyte that the present embodiment provides conductivity and electrochemical stability is at room temperature all better.
According to the method for embodiment 1, make and obtain all solid lithium secondary battery, from the electrochemical property test result of above-mentioned all solid lithium secondary battery electrolyte, gained all solid lithium secondary battery has good conductivity and electrochemical stability.
According to mol ratio, be 1:0.4:0.01, weigh purity and be respectively more than 99% Li
2s, P
2s
5with P
2o
5; Under argon gas atmosphere protection, in water content, be less than after above-mentioned raw materials being mixed under the condition of 100ppm and grind, then adopt high energy ball mill ball milling 40h, obtain just material;
Take out described just material, after being ground evenly, adopt the pressure of 10MPa to carry out compressing tablet, then the sheet obtaining is just expected to pack in quartz glass tube, be evacuated to after vacuum degree is less than 100Pa and use oxyhydrogen flame sealing by fusing, then the quartz glass tube that said mixture is housed is heated to 230 ℃, insulation 2h with the heating rate of 2 ℃/min, water-cooled cold quenching is to room temperature, under the condition that is 100ppm in water content, open pipe also grinds evenly again, obtains all solid lithium secondary battery electrolyte, i.e. P
2o
5the Li of doping
2s-P
2s
5system (70%Li
2s-29%P
2s
5-1%P
2o
5).
Obtain, after all solid lithium secondary battery electrolyte, according to the method for embodiment 1, it being carried out to XRD test.Test result shows, gained electrolyte is Li
1.4p
0.58s
2.17o
0.05.
And, according to the method for embodiment 1, described all solid lithium secondary battery electrolyte is carried out to chemical property and the test of air-stable performance.Test result demonstration, under the condition of 25 ℃, its lithium ion conductivity is 1.43 * 10
-3scm
-1, and there is the electrochemical window higher than 10V, show that all solid lithium secondary battery electrolyte that the present embodiment provides conductivity and electrochemical stability is at room temperature all better.
According to the method for embodiment 1, make and obtain all solid lithium secondary battery, from the electrochemical property test result of above-mentioned all solid lithium secondary battery electrolyte, gained all solid lithium secondary battery has good conductivity and electrochemical stability.
According to mol ratio, be 1:0.4:0.01, weigh purity and be respectively more than 99% Li
2s, P
2s
5with Li
2c
2; Under argon gas atmosphere protection, the high energy ball mill that under the condition that is 100ppm in water content, above-mentioned raw materials is placed in to sealing carries out ball milling, and ball milling 40h obtains all solid lithium secondary battery electrolyte, i.e. the Li of LiF doping
2s-P
2s
5system (70%Li
2s-29%P
2s
5-1%Li
2c
2).
Obtain, after all solid lithium secondary battery electrolyte, according to the method for embodiment 1, it being carried out to XRD test.Test result shows, gained electrolyte is Li
1.42p
0.58s
2.15c
0.02.
And, according to the method for embodiment 1, described all solid lithium secondary battery electrolyte is carried out to chemical property and the test of air-stable performance.Test result demonstration, under the condition of 25 ℃, its lithium ion conductivity is 1.06 * 10
-3scm
-1, and there is the electrochemical window higher than 10V, show that all solid lithium secondary battery electrolyte that the present embodiment provides conductivity and electrochemical stability is at room temperature all better.
According to the method for embodiment 1, make and obtain all solid lithium secondary battery, from the electrochemical property test result of above-mentioned all solid lithium secondary battery electrolyte, gained all solid lithium secondary battery has good conductivity and electrochemical stability.
According to mol ratio, be 1:0.4:0.01, weigh purity and be respectively more than 99% Li
2s, P
2s
5with B
2o
3; Under argon gas atmosphere protection, in water content, be less than after above-mentioned raw materials being mixed under the condition of 100ppm and grind, then adopt high energy ball mill ball milling 40h, obtain just material;
Take out described just material, after being ground evenly, adopt the pressure of 10MPa to carry out compressing tablet, then the sheet obtaining is just expected to pack in quartz glass tube, be evacuated to after vacuum degree is less than 100Pa and use oxyhydrogen flame sealing by fusing, then the quartz glass tube that said mixture is housed is heated to 300 ℃, insulation 2h with the heating rate of 2 ℃/min, water-cooled cold quenching is to room temperature, under the condition that is 100ppm in water content, open pipe also grinds evenly again, obtains all solid lithium secondary battery electrolyte, i.e. B
2o
3the Li of doping
2s-P
2s
5system (70%Li
2s-29%P
2s
5-1%B
2o
3).
Obtain, after all solid lithium secondary battery electrolyte, according to the method for embodiment 1, it being carried out to XRD test.Test result shows, gained electrolyte is Li
1.4p
0.58s
2.15b
0.02o
0.03.
And, according to the method for embodiment 1, described all solid lithium secondary battery electrolyte is carried out to chemical property and the test of air-stable performance.Test result demonstration, under the condition of 25 ℃, its lithium ion conductivity is 1.25 * 10
-3scm
-1, and there is the electrochemical window higher than 10V, show that all solid lithium secondary battery electrolyte that the present embodiment provides conductivity and electrochemical stability is at room temperature all better.
According to the method for embodiment 1, make and obtain all solid lithium secondary battery, from the electrochemical property test result of above-mentioned all solid lithium secondary battery electrolyte, gained all solid lithium secondary battery has good conductivity and electrochemical stability.
According to mol ratio, be 1:0.4:0.01, weigh purity and be respectively more than 99% Li
2s, P
2s
5with SeCl
4, under argon gas atmosphere protection, in water content, be less than under the condition of 100ppm after will above-mentioned raw materials mixing and carry out ball milling, then the raw material mixing is packed in quartz glass tube, be evacuated to after vacuum degree is less than 100Pa and use oxyhydrogen flame sealing by fusing, again the quartz glass tube that said mixture is housed is heated to 500 ℃ with the heating rate of 2 ℃/min, insulation 12h, cool to the furnace after room temperature, under the condition that is 100ppm in water content, open pipe also grinds evenly again, again pack in quartz glass tube subsequently, be evacuated to after vacuum degree is less than 100Pa and use oxyhydrogen flame sealing by fusing, heating rate with 2 ℃/min is heated to 260 ℃, insulation 2h, cool to the furnace after room temperature, open pipe grinding under the condition that is 100ppm in water content, obtain all solid lithium secondary battery electrolyte, be SeCl
4the Li of doping
2s-P
2s
5system (70%Li
2s-29%P
2s
5-1%SeCl
4).
Obtain, after all solid lithium secondary battery electrolyte, according to the method for embodiment 1, it being carried out to XRD test.Test result shows, gained electrolyte is Li
1.4p
0.58s
2.15se
0.01cl
0.04.
And, according to the method for embodiment 1, described all solid lithium secondary battery electrolyte is carried out to chemical property and the test of air-stable performance.Test result demonstration, under the condition of 25 ℃, its lithium ion conductivity is 1.53 * 10
-3scm
-1, and there is the electrochemical window higher than 10V, show that all solid lithium secondary battery electrolyte that the present embodiment provides conductivity and electrochemical stability is at room temperature all better.
According to mol ratio, be 1:0.4:0.01:0.01, weigh purity and be respectively more than 99% Li
2s, P
2s
5, B
2o
3with P
2o
5; Under argon gas atmosphere protection, in water content, be less than after above-mentioned raw materials being mixed under the condition of 100ppm and grind, then adopt high energy ball mill ball milling 40h, obtain just material;
Take out described just material, after being ground evenly, adopt the pressure of 10MPa to carry out compressing tablet, then the sheet obtaining is just expected to pack in quartz glass tube, be evacuated to after vacuum degree is less than 100Pa and use oxyhydrogen flame sealing by fusing, then the quartz glass tube that said mixture is housed is heated to 310 ℃, insulation 4h with the heating rate of 2 ℃/min, cool to the furnace after room temperature, under the condition that is 100ppm in water content, open pipe also grinds evenly again, obtains all solid lithium secondary battery electrolyte, i.e. B
2o
3with P
2o
5the Li of doping
2s-P
2s
5system.
Obtain, after all solid lithium secondary battery electrolyte, according to the method for embodiment 1, it being carried out to XRD test.Test result shows, gained electrolyte is Li
1.4p
0.58s
2.1b
0.02o
0.08.
And, according to the method for embodiment 1, described all solid lithium secondary battery electrolyte is carried out to chemical property and the test of air-stable performance.Test result demonstration, under the condition of 25 ℃, its lithium ion conductivity is 2.15 * 10
-3scm
-1, and there is the electrochemical window higher than 10V, show that all solid lithium secondary battery electrolyte that the present embodiment provides conductivity and electrochemical stability is at room temperature all better.
According to the method for embodiment 1, make and obtain all solid lithium secondary battery, from the electrochemical property test result of above-mentioned all solid lithium secondary battery electrolyte, gained all solid lithium secondary battery has good conductivity and electrochemical stability.
Embodiment 8
According to mol ratio, be 1:0.4:0.01, weigh purity and be respectively more than 99% Li
2s, P
2s
5with LiCl; Under argon gas atmosphere protection, the high energy ball mill that under the condition that is 100ppm in water content, above-mentioned raw materials is placed in to sealing carries out ball milling, and ball milling 40h obtains all solid lithium secondary battery electrolyte, i.e. the Li of LiCl doping
2s-P
2s
5system (70%Li
2s-29%P
2s
5-1%LiCl).
Obtain, after all solid lithium secondary battery electrolyte, according to the method for embodiment 1, it being carried out to XRD test.Test result shows, gained electrolyte is Li
1.41p
0.58s
2.15cl
0.01.
And, according to the method for embodiment 1, described all solid lithium secondary battery electrolyte is carried out to chemical property and the test of air-stable performance.Test result demonstration, under the condition of 25 ℃, its lithium ion conductivity is 1.15 * 10
-3scm
-1, and there is the electrochemical window higher than 10V, show that all solid lithium secondary battery electrolyte that the present embodiment provides conductivity and electrochemical stability is at room temperature all better.
According to the method for embodiment 1, make and obtain all solid lithium secondary battery, from the electrochemical property test result of above-mentioned all solid lithium secondary battery electrolyte, gained all solid lithium secondary battery has good conductivity and electrochemical stability.
Embodiment 9
According to mol ratio, be 1:0.4:0.01, weigh purity and be respectively more than 99% Li
2s, P
2s
5with LiBr, under argon gas atmosphere protection, in water content, be less than under the condition of 100ppm after will above-mentioned raw materials mixing and carry out ball milling, then the raw material mixing is packed in quartz glass tube, be evacuated to after vacuum degree is less than 100Pa and use oxyhydrogen flame sealing by fusing, again the quartz glass tube that said mixture is housed is heated to 450 ℃ with the heating rate of 2 ℃/min, insulation 12h, water-cooled cold quenching is to room temperature, under the condition that is 0.1ppm in water content, open pipe grinding are evenly, and then pack in quartz glass tube, be evacuated to after vacuum degree is less than 100Pa and use oxyhydrogen flame sealing by fusing, again the quartz glass tube that said mixture is housed is heated to 230 ℃ with the heating rate of 2 ℃/min, insulation 4h, cool to the furnace after room temperature, under the condition that is 100ppm in water content, open pipe also grinds evenly again, obtain all solid lithium secondary battery electrolyte, be the Li of LiBr doping
2s-P
2s
5system (70%Li
2s-29%P
2s
5-1%LiBr).
Obtain, after all solid lithium secondary battery electrolyte, according to the method for embodiment 1, it being carried out to XRD test.Test result shows, gained electrolyte is Li
1.41p
0.58s
2.15br
0.01.
And, according to the method for embodiment 1, described all solid lithium secondary battery electrolyte is carried out to chemical property and the test of air-stable performance.Test result demonstration, under the condition of 25 ℃, its lithium ion conductivity is 1.36 * 10
-3scm
-1, and there is the electrochemical window higher than 10V, show that all solid lithium secondary battery electrolyte that the present embodiment provides conductivity and electrochemical stability is at room temperature all better.
According to the method for embodiment 1, make and obtain all solid lithium secondary battery, from the electrochemical property test result of above-mentioned all solid lithium secondary battery electrolyte, gained all solid lithium secondary battery has good conductivity and electrochemical stability.
The lithium ion conductivity of all solid lithium secondary battery electrolyte that as seen from the above embodiment, the embodiment of the present invention provides is at room temperature up to～10
-3scm
-1, there is good conductivity.And it has the electrochemical window higher than 10V, with respect to hyperoxia voltinism positive electrode and high reproducibility negative material, there is good stability, electrochemical stability is better.In addition, its air stability is better, and cost is lower, is beneficial to application, is especially applicable to being applied in the solid state battery system of high power density.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection range of the claims in the present invention.
Claims (9)
1. all solid lithium secondary battery electrolyte shown in formula (I):
Li
aP
bS
cM
d（I）；
In formula (I), M is one or more in III, IV, V, VI and VII main group nonmetalloid; 0 < a≤10,0 < b≤5,0 < c≤15,0 < d < 1.
2. all solid lithium secondary battery electrolyte according to claim 1, is characterized in that, M is one or more in boron element, carbon, nitrogen element, oxygen element, selenium element, chlorine element, bromo element and I.
3. a preparation method for all solid lithium secondary battery electrolyte, comprising:
By Li
2s, P
2s
5after mixing with alloy, grind, the time of described grinding is 5h at least, obtains all solid lithium secondary battery electrolyte;
Described alloy is III, IV, V, VI and the VII main group nonmetalloid compound of lithium, and one or more in the compound that at least two elements form in III, IV, V, VI and VII main group nonmetalloid.
4. preparation method according to claim 3, it is characterized in that, described alloy is one or more in lithium chloride, lithium bromide, lithium iodide, boronation lithium, lithium carbide, lithium nitride, lithia, lithium selenide, phosphorus nitride, selenium chloride, boron oxide and phosphorous oxide.
5. preparation method according to claim 3, is characterized in that, described Li
2s, P
2s
5with the mol ratio of alloy be 1:(0.01～1): (0.001～0.1).
6. preparation method according to claim 3, is characterized in that, described in be ground to high-energy ball milling, rotating speed is 200rpm～600rpm, the time is 6h～60h, ratio of grinding media to material is 1:1～60:1.
7. preparation method according to claim 3, is characterized in that, by Li
2s, P
2s
5after grinding with the mixture of alloy, also comprise:
Mixture after grinding is heat-treated, and described heat treated temperature is 100 ℃～500 ℃, obtains all solid lithium secondary battery electrolyte.
8. preparation method according to claim 3, is characterized in that, described grinding is carried out under inert atmosphere, and the water content of described inert atmosphere is less than 100ppm, and oxygen content is less than 100ppm.
9. an all solid lithium secondary battery, comprise positive pole, negative pole and all solid lithium secondary battery electrolyte, it is characterized in that, described all solid lithium secondary battery electrolyte is all solid lithium secondary battery electrolyte described in claim 1 or 2 or all solid lithium secondary battery electrolyte prepared according to the preparation method described in claim 3～8 any one.
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