CN109713361A - A kind of NASICON type solid electrolyte material and preparation method thereof - Google Patents
A kind of NASICON type solid electrolyte material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 22
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 14
- 239000002228 NASICON Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000003980 solgel method Methods 0.000 claims abstract description 9
- 230000006872 improvement Effects 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims description 41
- 239000000843 powder Substances 0.000 claims description 19
- 229910019142 PO4 Inorganic materials 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 230000007704 transition Effects 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 150000003609 titanium compounds Chemical class 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- -1 phosphorus compound Chemical class 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- MKGYHFFYERNDHK-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Ti+4].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[Li+] MKGYHFFYERNDHK-UHFFFAOYSA-K 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 150000001399 aluminium compounds Chemical class 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 238000005660 chlorination reaction Methods 0.000 claims 2
- 150000003624 transition metals Chemical class 0.000 claims 2
- 229960000583 acetic acid Drugs 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000001257 actinium Chemical class 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000012362 glacial acetic acid Substances 0.000 claims 1
- 150000002642 lithium compounds Chemical class 0.000 claims 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 229920002647 polyamide Polymers 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
- 150000008442 polyphenolic compounds Polymers 0.000 claims 1
- 235000013824 polyphenols Nutrition 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims 1
- 229910000314 transition metal oxide Inorganic materials 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002001 electrolyte material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 5
- 235000015165 citric acid Nutrition 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000002847 impedance measurement Methods 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003020 moisturizing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 description 1
- 229910009274 Li1.4Al0.4Ti1.6 (PO4)3 Inorganic materials 0.000 description 1
- 229910000857 LiTi2(PO4)3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 241001282153 Scopelogadus mizolepis Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052767 actinium Inorganic materials 0.000 description 1
- QQINRWTZWGJFDB-UHFFFAOYSA-N actinium atom Chemical compound [Ac] QQINRWTZWGJFDB-UHFFFAOYSA-N 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of NASICON type solid electrolyte material, chemical formula is represented by Li1+x Al y (Ti1‑z M z )2‑y (PO4)3.The solid electrolyte material has good ionic conductance characteristic, and electrolyte can be fabricated separately.The electrolyte has good mechanical property simultaneously, can be used in mixed way with other series of electrolyte materials, to promote the macrostructure stability of other series of electrolyte.The present invention discloses the improvement sol-gel method for preparing the solid electrolyte material, process is simple, low raw-material cost, is easy to scale of mass production popularization.
Description
Invention field
The present invention relates to a kind of NASICON type solid electrolyte materials and preparation method thereof, are specifically related to a kind of chemistry
Formula is Li1+xAly(Ti1-zMz)2-y(PO4)3Solid electrolyte material and preparation method thereof.
Background technique
The electrolyte used of commercialization lithium battery is liquid electrolyte at present, has ionic conductivity height, charge/discharge speed
The advantages such as fast, but there is also following disadvantages: 1. liquid electrolytes are inflammable, and there are direct security risks；2. easily with electrolysis material
Interfacial reaction occurs for material, reduces specific capacity and cycle characteristics；3. otherwise cannot easily be formed with metal Li directly as negative electrode material
Li dendrite pierces through diaphragm, causes the danger of short circuit and explosion.
Solid lithium battery using solid material as electrolyte is widely recognized as next-generation lithium battery, in safety factor
Aspect is greatly improved.In all kinds of inorganic solid electrolyte materials, NASICON profile material has following advantage: 1. raw material
It is at low cost；2. high-temperature stability is good；3. not reacting with water, it is easy to save under atmospheric environment；4. allowing to use lithium metal as negative
Pole material will not promote the formation of Li dendrite.NASICON originally means super ion conductor Na1+mZr2SimP3-mO12(0 < m <
3).Broadly, when Na, Zr, Si are replaced by same valence element, material is referred to as NASICON type.
LiTi2(PO4)3It (LTP) is typical NASICON profile material, undoped LTP conductivity is 10-6S/cm, cannot
Directly meet lithium battery to the requirement of electrolyte.Therefore, it is necessary to be doped modification to LTP.Common doped chemical
For Al, there is certain effect to conductivity is promoted.But with the promotion of doping content, easily there is the second phase AlPO4, destroy electricity
Solve the original crystal structure of matter.
Based on there are many common preparation methods of LTP electrolyte, comprising: solid reaction process, hydro-thermal method, colloidal sol-are solidifying
Glue method, coprecipitation etc..Solid reaction process process is simple, but high-energy ball milling is needed early period to realize mechanical alloying, is not suitable for big
Scale volume production；Hydro-thermal method and the powder constituents of coprecipitation preparation are uniform but higher to reaction kettle equipment requirement；Traditional is molten
Glue-gel method is usually to mix raw material uniformly, and hydrolysis, condensation occurs etc. to react and formed transparent molten
Colloid forms three-dimensional netted gelinite finally by drying.The powder constituents of traditional sol-gel method preparation are uniform, and
It is of less demanding to consersion unit, but initial reaction stage severe reaction conditions, excessively rely on the control to pH value, it is not easy to obtain single-phase
Powder, and solvent used is usually organic solvent, at high cost.
Summary of the invention
The present invention proposes improvement to traditional sol-gel method, referred to as improvement sol-gel method.This method and tradition
Sol-gel method be compared to characteristic: do not need to be previously added a large amount of ammonium hydroxide in the solution and improve citric acids to each source metal
Complexation efficiency, it is only necessary to a small amount of citric acid is added, titanium source is prevented quickly to reunite generation white precipitate, therefore this method is to anti-
During answering pH variation and it is insensitive, process be simply easy to volume production popularization.This method is easier to obtain single-phase LTP base electrolysis
Material.The LTP original washing powder body sintering activity of this method preparation is more preferable, it is easier to obtain fine and close ceramic body and good ion is led
Electrical characteristics.
The present invention proposes a kind of complex element to Ti methods being doped of LTP electrolyte, and this method compares unit
Element doping can more effectively improve the conductivity of electrolyte.Complex element includes metal element A l and transition metal element
Collocation uses.
Wherein NASICON type electrolyte, element composition have Li, Al, Ti, M, P, O.Wherein M is transition element,
It may is that the first subgroup element, the second subgroup element, third subgroup element (including group of the lanthanides and actinium series), the 4th subgroup element,
Five subgroup elements, the 6th subgroup element, the 7th subgroup element, one of or several combination in the 8th subgroup element, knot
Structure basic material is titanium phosphate lithium (LTP), and chemical formula can be expressed as formula (1).
Li1+xAly(Ti1-zMz)2-y(PO4)3 (1)
In above-mentioned formula (1), 0≤x≤1,0 z≤1 the < < of y≤1, x-y≤0.1,0.
The atomic radius ratio of above-mentioned transition element M, atomic radius and Ti are RM/RTi.In order to maintain NASICON type
Crystal structure works as RM/RTi> 1.1 or RM/RTiWhen < 0.9, z value range is 0 z≤0.5 <.As 0.9≤RM/R-Ti≤1.1
When, z value range is 0 z≤1 <.
Preferably, transition element M, when its highest oxidation state is 4 valence of ﹢ and 0.9≤RM/RTiWhen≤1.1,0 z≤1 <,
Such as Li1+xAly(Ti0.5Zr0.5)2-y(PO4)3.Reach a small number of rare earth element (Ce, Pr, Nd, the Tb of 4 valence of ﹢ for highest oxidation state
And Dy), RM/RTi1.1,0 z≤0.5 < >, such as Li1+xAly(Ti0.5Ce0.5)2-y(PO4)3。
Preferably, the transition element M, when its highest oxidation state is higher than 4 valence of ﹢ and 0.9≤RM/RTiWhen≤1.1,
0 z≤0.5 <, such as Li1+xAly(Ti0.5V0.5)2-y(PO4)3.When its highest oxidation state is higher than 4 valence of ﹢ and RM/RTiWhen < 0.9,
0 z≤0.25 <, such as Li1+xAly(Ti0.75Mn0.25)2-y(PO4)3。
Preferably, the transition element M, when its highest oxidation state is lower than 4 valence of ﹢ and 0.9≤RM/RTiWhen≤1.1,
0 z≤0.5 <, such as Li1+xAly(Ti0.5Sc0.5)2-y(PO4)3.When its highest oxidation state is lower than 4 valence of ﹢ and RM/RTi> 1.1
When, 0 z≤0.25 <, such as Li1+xAly(Ti0.75Y0.25)2-y(PO4)3.When its highest oxidation state is lower than 4 valence of ﹢ and RM/RTi<
When 0.9,0 z≤0.25 <, such as Li1+xAly(Ti0.75Co0.25)2-y(PO4)3。
Preferably, in the case that the transition element M highest oxidation state is 4 valence of ﹢, element Li in formula (1) with
The relation with contents of element al are as follows: 0≤x-y≤0.05.
Preferably, in the case that the transition element M highest oxidation state is higher than 4 valence of ﹢, the element Li in formula (1)
With the relation with contents of element al are as follows: x-y≤0.The relation with contents of element Li and element al in formula (1) are as follows: x-y≤0.
Preferably, in the case that the transition element M highest oxidation state is lower than 4 valence of ﹢, the element Li in formula (1)
With the relation with contents of element al are as follows: 0 x-y≤0.1 <.
Li is prepared using sol-gel method is improved1+xAly(Ti1-zMz)2-y(PO4)3Powder step includes:
1) complexing agent and water are added into container, after completely dissolution to complexing agent, lithiumation conjunction is proportionally added into solution
Object, aluminium compound, phosphorus compound, transistion metal compound, titanium compound (raw material finally added is titanium compound).Addition
While not stopping stirring in the process, and add titanium compound, moisture content is supplemented into solution, and (supplement moisture content weight is complexing agent
1~2 times).Continue 2~4h of agitating solution, obtains milky white solution.
2) above-mentioned milky white solution is dry at 75~110 DEG C, obtain sticky gel；It is carried out again at 200~550 DEG C
2~4h of precalcining；Finally in 700~850 DEG C of 4~6h of calcining, porous white wadding body is obtained.
3) obtained porous white block is put into high-speed mixer, crushed, after sieving.Obtain even-grained white powder
End.
The Li obtained according to above-mentioned steps1+xAly(Ti1-zMz)2-y(PO4)3Powder granularity is in 300 mesh.
The present invention also utilizes above-mentioned Li1+xAly(Ti1-zMz)2-y(PO4)3Powder is prepared for solid electrolyte, by powder 30
Cold moudling under~300MPa obtains round green body having a size of 10~16mm of diameter, 1~2mm of thickness, then 700~1000
DEG C sinter ceramics into.Potsherd total conductivity obtained is up to 10-4S/cm。
Detailed description of the invention
Fig. 1 improves sol-gel method flow chart.
Fig. 2 X-ray diffractogram spectrum analysis white powder component, obtained map and titanium phosphate lithium standard card (PDF35-
0754) it compares without obvious dephasign peak.
Fig. 3 scanning electron microscope analysis white powder pattern.
Fig. 4 potsherd ac impedance spectroscopy.
Case study on implementation
Case study on implementation 1. is according to Li1.4Al0.4Ti1.6(PO4)3Stoichiometric ratio, take citric acid 55.38g be added 41.52g
It is sufficiently dissolved in water；Take 6.76g lithium nitrate, nine water aluminum nitrate of 10.5g, 24.15g ammonium dihydrogen phosphate addition aqueous solution sufficiently molten
Solution；Butyl titanate 38.08g is taken to be slowly added to above-mentioned mixed solution, while the moisturizing 60g into solution.It is stirred to react 4h, is obtained newborn
The solution of white.
Above-mentioned milky white solution is dried into 3h at 110 DEG C, obtains sticky gel；Again in 400 DEG C of precalcining 4h；Finally
In 800 DEG C of calcining 4h, white wadding body is obtained.It is crushed by high speed disintegrator, after sieving, obtains white powder.
It is 10mm, with a thickness of the disk of 1.5mm that white powder, which is depressed to diameter in the pressure of 46MPa,.Then at 880 DEG C
It is sintered 5h, obtains potsherd.Potsherd is connected on electrochemical operation and carries out ac impedance measurement.Electrochemical workstation test
Frequency range 100Hz~1MHz obtains the total conductivity of potsherd are as follows: 1 × 10-4S/cm。
Case study on implementation 2. is according to Li1.3Al0.3Ti1.7(PO4)3Stoichiometric ratio, take citric acid 221.52g be added
166.08g sufficiently being dissolved in water；27.04g lithium nitrate, nine water aluminum nitrate of 33.95g, 104.1g ammonium dihydrogen phosphate is taken to be added water-soluble
Liquid sufficiently dissolves；Butyl titanate 174.53g is taken to be slowly added to above-mentioned mixed solution, while the moisturizing 300g into solution.Stirring
4h is reacted, opalescent solution is obtained.
Above-mentioned milky white solution is dried into 3h at 110 DEG C, obtains sticky gel；Again in 450 DEG C of precalcining 4h；Finally
In 850 DEG C of calcining 5h, white wadding body is obtained.It is crushed by high speed disintegrator, after sieving, obtains white powder.
It is 10mm, with a thickness of the disk of 1.5mm that white powder, which is depressed to diameter in the pressure of 46MPa,.Then at 880 DEG C
It is sintered 5h, obtains potsherd.Potsherd is connected on electrochemical operation and carries out ac impedance measurement.Electrochemical workstation test
Frequency range 100Hz~1MHz obtains the total conductivity of potsherd are as follows: 1 × 10-4S/cm。
Case study on implementation 3~8, reference table 1
Table 1 improves sol-gel method and prepares solid electrolyte material case study on implementation
Applicant combines Figure of description to be described in detail and describe the embodiment of the present invention, but this field skill
Art personnel are it should be understood that above embodiments are only the preferred embodiments of the invention, and explanation is intended merely to help reader in detail
More fully understand spirit of that invention, and it is not intended to limit the protection scope of the present invention, on the contrary, any based on invention essence of the invention
Any improvement or modification made by mind should all be fallen within the scope and spirit of the invention.
Claims (13)
1. a kind of NASICON type solid electrolyte material, element composition has Li, Al, Ti, M, P, O；Wherein M is transition group member
Element, may is that the first subgroup element, the second subgroup element, third subgroup element, including group of the lanthanides and actinium series, the 4th subgroup element,
5th subgroup element, the 6th subgroup element, the 7th subgroup element, one of or several combination in the 8th subgroup element；Its
Structure basis material is titanium phosphate lithium (LTP), and chemical formula can be expressed as following structure fomula (1)
Li1+xAly(Ti1-zMz)2-y(PO4)3 (1)。
2. in formula described in claim 1 (1), 0≤x≤1,0 z≤1 the < < of y≤1, x-y≤0.1,0.
3. the atomic radius ratio of transition element M described in claim 1, atomic radius and Ti are RM/RTi.In order to maintain
NASICON type crystal structure, works as RM/RTi> 1.1 or RM/RTiWhen < 0.9, z value range is 0 z≤0.5 <, as 0.9≤RM/
RTiWhen≤1.1, z value range is 0 z≤1 <.
4. transition element M as claimed in claim 3, when its highest oxidation state is higher than 4 valence of ﹢ and RM/RTiWhen < 0.9,0 < z
≤0.25。
5. transition element M as claimed in claim 3, when its highest oxidation state is lower than 4 valence of ﹢ and RM/RTi> 1.1 or
RM/RTiWhen < 0.9,0 z≤0.25 <.
In the case that 6. transition element M highest oxidation state as claimed in claim 3 is 4 valence of ﹢, element Li in formula (1) with
The relation with contents of element al are as follows: 0≤x-y≤0.05.
In the case that 7. transition element M highest oxidation state as claimed in claim 3 is higher than 4 valence of ﹢, the element Li in formula (1)
With the relation with contents of element al are as follows: x-y≤0.
In the case that 8. transition element M highest oxidation state as claimed in claim 3 is lower than 4 valence of ﹢, the element Li in formula (1)
With the relation with contents of element al are as follows: 0 x-y≤0.1 <.
9. a kind of method for preparing NASICON type solid electrolyte material improves sol-gel method, step includes: the first step,
Dissolution of raw material mixing, is added complexing agent into container and water after completely dissolution to complexing agent is proportionally added into lithiumation into solution
Object, aluminium compound, phosphorus compound, transistion metal compound, titanium compound are closed, is persistently stirred during addition；
The solution that the first step obtains is dried in second step, obtains sticky gel；
Third step is further dried and carries out multisection type calcining, obtains white fluffy solid；
4th step, it is Li that crushing, which obtains chemical formula,1+xAly(Ti1-zMz)2-y(PO4)3Powder.
5th step, Li1+xAly(Ti1-zMz)2-y(PO4)3Powder obtains solid electrolyte by cold pressing, sintering.It can also be by Li1+xAly
(Ti1-zMz)2-y(PO4)3Powder is mixed with the high molecular material with ionic conduction characteristic, then is cold-pressed and solid electrolyte is made.
10. improvement sol-gel the preparation method as claimed in claim 9 prepares Li1+xAly(Ti1-zMz)2-y(PO4)3Used in powder
Raw material include:
Complexing agent selects one of citric acid, glacial acetic acid；
Lithium compound, one of selective chlorination lithium, lithium nitrate, lithium sulfate, lithium hydroxide and its hydrate；
Aluminium compound, one of selective chlorination aluminium, aluminum nitrate, aluminum sulfate, aluminium hydroxide and its hydrate；
Phosphorus compound selects one of ammonium dihydrogen phosphate, phosphoric acid；
Transistion metal compound selects transition metal oxide, transition metal salt, transition metal hydroxide, transition metal
One of esters；
Titanium compound selects one of butyl titanate, metatitanic acid.
11. improvement sol-gel the preparation method as claimed in claim 9, the sequence of Xiang Shuizhong adding raw materials: is added into water first
Raw material be complexing agent, the raw material being finally added into solution is titanium compound.
12. the multisection type calcining: improvement sol-gel the preparation method as claimed in claim 9 must have before final calcining
The precalcining at least one stage, 200-550 DEG C of precalcining temperature range.
13. as claimed in claim 9 and with ionic conduction characteristic high molecular material includes polyethers, polyurethanes, poly- phenol
It is class, polyamide-based one such or a variety of.
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| CN113346127A (en) * | 2021-05-31 | 2021-09-03 | 东风汽车集团股份有限公司 | NASICON type lithium ion solid electrolyte, preparation method and battery |
| CN115849329A (en) * | 2022-12-29 | 2023-03-28 | 宜宾南木纳米科技有限公司 | Europium-doped lithium aluminum titanium phosphate solid electrolyte material and preparation method and application thereof |
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