CN110212240A - Lithium ion solid electrolyte and preparation method thereof - Google Patents

Lithium ion solid electrolyte and preparation method thereof Download PDF

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Publication number
CN110212240A
CN110212240A CN201910562448.5A CN201910562448A CN110212240A CN 110212240 A CN110212240 A CN 110212240A CN 201910562448 A CN201910562448 A CN 201910562448A CN 110212240 A CN110212240 A CN 110212240A
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China
Prior art keywords
solid electrolyte
lithium ion
lithium
preparation
ion solid
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Inventor
汤卫平
李文磊
张竞择
王琴
朱蕾
吴勇民
贾荻
吴晓萌
田文生
陈玉华
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Shanghai Institute of Space Power Sources
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Shanghai Institute of Space Power Sources
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    • 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
    • H01M10/056—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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Conductive Materials (AREA)

Abstract

The present invention relates to a kind of lithium ion solid electrolytes and preparation method thereof, belong to solid state lithium battery field.The present invention is prepared for a kind of novel Li superionic conductors Li1+xZr2P3‑xSixO12(0≤x≤3), are applicable to the solid electrolyte of solid state battery, and ionic conductivity is greater than 10‑3S/cm, electrochemical stability is good, and the stability without side reaction, while in air environment is good, and processing performance is good in solid state battery preparation process, and machinery, the chemical compatibility with electrode material are good.

Description

Lithium ion solid electrolyte and preparation method thereof
Technical field
The present invention relates to a kind of lithium ion solid electrolytes and preparation method thereof, belong to lithium ion solid electrolyte technology neck Domain.
Background technique
Lithium ion battery is the highest energy storage device of current energy density, but energy density gradually reaches the upper limit, and The raising of energy density is so that the safety issue of lithium ion battery becomes increasingly conspicuous.Solid state battery is expected to become than lithium ion battery More high-energy-density density, safer energy storage device.The performance of solid electrolyte is the most key of decision solid state battery performance Factor.
In the prior art, although the electronic conductivity of the solid electrolyte of sulphur system and anti-perovskite structure can achieve 10- 2S/cm, but there are the following problems:
1, poor chemical stability；
2, electrochemical stability is poor；
3, poor processability.
Summary of the invention
Technology of the invention solves the problems, such as: overcome the deficiencies in the prior art, propose a kind of lithium ion solid electrolyte and Preparation method, lithium ion solid electrolyte chemical stability, electrochemical stability and the good operation performance, and ionic conductivity It is high (to be greater than 10-3S/cm)。
The technical solution of the invention is as follows:
A kind of lithium ion solid electrolyte, the solid electrolyte are Li superionic conductors, chemical formula Li1+xZr2P3- xSixO12, 0≤x≤3, preferably Li3Si2Zr2PO12。
A kind of the step of preparation method of lithium ion solid electrolyte, this method includes:
(1) Na superionic conductors powder is put into the solution containing Li ion, is heated, stirring, in heating stirring mistake The exchange reaction that Na ion and Li ion occur in journey, obtains mixture；
(2) mixture that step (1) obtains is filtered, then cleans filter cake, obtain Li superionic conductors Powder, and Li superionic conductors powder alcohol or distilled water are cleaned repeatedly, obtain pure Li superionic conductors powder；
(3) the pure Li superionic conductors powder that step (2) obtains is heat-treated, obtains lithium ion solid state electrolysis Matter.
In the step (1), the chemical formula of Na superionic conductors powder is Na1+xZr2P3-xSixO12, 0≤x≤3 are excellent Select Na3Si2Zr2PO12、Na4Zr2(SiO4)3、NaZr2(PO4)3、Na3Hf2Si2PO12、Na3La(PO4)2、Na1.3Ti1.7Al0.3 (PO4)3、Na3V2(PO4)3、Na2.96Nb0.04Zr1.96Si2PO12；
In the step (1), in the solution of Li ion, solvent is ionic liquid, ionic liquid C6H11BF4N2、 C8H20BF4NO、C7H16BF4N、C8H11F6N3O4S2、C8H16F6N2O4S2、C6H11F2N3O4S2Or C9H20F2N2O4S2；Generate li ion Lithium salts be LiClO4、LiPF6、LiNO3, LiCl, LiBF4, LiTFSI, LiBOB, LiDFOB or LiFSI；
In the step (1), heating temperature is 50-400 DEG C, mixing time 2-100h；
In the step (2), when being cleaned, cleaned using methanol, ethyl alcohol or deionized water；
In the step (3), heat treatment temperature be 300-900 DEG C, preferably 300-700 DEG C, heat treatment time 2- 10h。
A kind of the step of preparation method of lithium ion solid electrolyte, this method includes:
(1) Na superionic conductors and Li salt are mixed, then carrying out heating stirring to Li salt is molten condition, is being added The exchange reaction that Na ion and Li ion occur during thermal agitation, is down to room temperature, obtains Li superionic conductors/lithium fused salt mixing Object；
(2) Li superionic conductors/lithium molten salt mixture and distilled water/alcohol that step (1) obtains are mixed, makes to steam Distilled water/alcohol dissolves lithium fused salt, then filters, and filter cake is cleaned, and obtains Li superionic conductors powder, and Li is surpassed Ion conductor powder alcohol or distilled water clean repeatedly, obtain pure Li superionic conductors powder；
(3) the pure Li superionic conductors powder that step (2) obtains is heat-treated, obtains lithium ion solid state electrolysis Matter.
In the step (1), the chemical formula of Na superionic conductors powder is Na1+xZr2P3-xSixO12, 0≤x≤3 are excellent Select Na3Si2Zr2PO12、Na4Zr2(SiO4)3、NaZr2(PO4)3、Na3Hf2Si2PO12、Na3La(PO4)2、Na1.3Ti1.7Al0.3 (PO4)3、Na3V2(PO4)3、Na2.96Nb0.04Zr1.96Si2PO12；
In the step (1), lithium salts is inorganic lithium salts or these salt such as lithium chloride, lithium nitrate, lithium sulfate, lithium hydroxide Mixture, as long as the lithium salts that can be melted at a high temperature of certain can be selected；
In the step (1), heating temperature can generally be selected in fusing point or more depending on the fusing point of the lithium salts of selection In the range of 50-150 degree, mixing time exchanges degree according to Li/Na and determines, is usually no more than 100h, preferably 2-100h；
In the step (2), when being cleaned, cleaned using methanol, ethyl alcohol or deionized water；
In the step (3), heat treatment temperature be 300-900 DEG C, preferably 300-700 DEG C, heat treatment time 2- 10h。
Beneficial effect
(1) ionic conductivity of the invention to solid electrolyte is greater than 10-3S/cm, electrochemical stability will get well, not have Side reaction, while processing performance is good in solid state battery preparation process, machinery, the chemical compatibility with electrode material are good.
(2) the invention proposes, to synthesize lithium superionic conductors, pass through by sodium superionic conductors (NASICON) structure NASICON is put into the solvent or fused salt containing lithium ion, allows it that the exchange reaction of sodium and lithium ion occurs, forms class The LISICON lithium ion conductor of NASICON structure；
(3) composite solid state sodium ion conductor (NASICON) first in the present invention, then in the solvent of lithium ion or fused salt Carry out sodium/lithium ion ion-exchange reactions, synthesizing lithium ion conductor (LISICON).Obtained lithium ion conductor inherits sodium The structure of ion conductor, it is shown that ionic conductivity equivalent or higher than sodium ion conductor, the lithium ion conductor are shown to lithium The good stability of metal is excellent lithium ion solid electrolyte.
Detailed description of the invention
Fig. 1 is Na3Si2Zr2PO12Li is exchanged with ionic liquid3Si2Zr2PO12XRD spectrum.
Fig. 2 is Na3Si2Zr2PO12Li is exchanged with fused salt3Si2Zr2PO12XRD spectrum.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples.
Embodiment 1
A kind of lithium ion solid electrolyte, the solid electrolyte are Li3Si2Zr2PO12。
A kind of the step of preparation method of lithium ion solid electrolyte, this method includes:
(1) by 0.71g Na3Si2Zr2PO12It is put into the ionic liquid C containing 5.74g8H11F6N3O4S2In, wherein ionic liquid Body is solvent, is then heated to 100 DEG C, stirs 10h, and Na ion occurs during heating stirring and exchanging for Li ion is anti- It answers, obtains mixture；
(2) mixture that step (1) obtains is filtered, filter cake is cleaned with deionized water then, obtains Li Superionic conductors；
(3) the Li superionic conductors that step (2) obtains is carried out being heat-treated 5h at 300 DEG C, obtains lithium ion solid-state electricity Solve matter Li3Si2Zr2PO12。
Obtained lithium ion solid electrolyte Li3Si2Zr2PO12XRD spectra and Na3Si2Zr2PO12It is common such as Fig. 1 institute Show；
Obtained lithium ion solid electrolyte Li3Si2Zr2PO12Ionic conductivity be 6.7x10-3S/cm。
Embodiment 2
A kind of lithium ion solid electrolyte, the solid electrolyte are Li3Si2Zr2PO12。
A kind of the step of preparation method of lithium ion solid electrolyte, this method includes:
(1) by 1g Na3Si2Zr2PO12It is added to 10g LiNO3In, it is fully ground mixing, forms homogeneous mixture；
(2) mixture of step (1) is then heated to 350 DEG C, is cooled to room temperature after keeping the temperature 20h；
(3) deionized water will be added in mixture that step (2) obtains, waits LiNO3After completely dissolution, it filters.It obtains Filter cake carries out cleaning 3 times with distilled water, at the Li superionic conductors that 100 degree of drying steps (3) obtain 10 hours, obtains Li solid-state Electrolyte；
(4) step (3) is obtained into Li solid electrolyte at 300 DEG C and is heat-treated 5h, obtain the lithium ion solid-state of weight crystallization Electrolyte Li3Si2Zr2PO12。
Obtained lithium ion solid electrolyte Li3Si2Zr2PO12XRD spectra and Na3Si2Zr2PO12It is common such as Fig. 2 institute Show；
Obtained lithium ion solid electrolyte Li3Si2Zr2PO12Ionic conductivity be 7x10-3S/cm。

Claims (10)

1. a kind of lithium ion solid electrolyte, it is characterised in that: the solid electrolyte is Li superionic conductors, chemical formula Li1+ xZr2P3-xSixO12, 0≤x≤3.
2. a kind of lithium ion solid electrolyte according to claim 1, it is characterised in that: solid electrolyte is Li3Si2Zr2PO12。
3. a kind of preparation method of lithium ion solid electrolyte, it is characterised in that the step of this method includes:
(1) Na superionic conductors powder and Li salt are mixed, then carrying out heating stirring to Li salt is molten condition, then It is down to room temperature, obtains Li superionic conductors/lithium molten salt mixture；
(2) Li superionic conductors/lithium molten salt mixture that step (1) obtains is mixed with distilled water or alcohol, makes to distill Water/alcohol dissolves lithium fused salt, then filters, and filter cake is cleaned, and obtains Li superionic conductors powder, and by Li surpass from Sub- conductor powder alcohol or distilled water clean repeatedly, obtain pure Li superionic conductors powder；
(3) the pure Li superionic conductors powder that step (2) obtains is heat-treated, obtains lithium ion solid electrolyte.
4. a kind of preparation method of lithium ion solid electrolyte according to claim 3, it is characterised in that: the step (1) in, the chemical formula of Na superionic conductors powder is Na1+xZr2P3-xSixO12, 0≤x≤3.
5. a kind of preparation method of lithium ion solid electrolyte according to claim 4, it is characterised in that: Na super-ionic is led Body powder is Na3Si2Zr2PO12、Na4Zr2(SiO4)3、NaZr2(PO4)3、Na3Hf2Si2PO12、Na3La(PO4)2、 Na1.3Ti1.7Al0.3(PO4)3、Na3V2(PO4)3Or Na2.96Nb0.04Zr1.96Si2PO12。
6. a kind of preparation method of lithium ion solid electrolyte according to claim 3, it is characterised in that: the step (1) in, lithium salts is the mixture of one or more of lithium chloride, lithium nitrate, lithium sulfate, lithium hydroxide.
7. a kind of preparation method of lithium ion solid electrolyte according to claim 3, it is characterised in that: the step (1) in, heating temperature is within the scope of the above 50-150 degree of lithium salts fusing point.
8. a kind of preparation method of lithium ion solid electrolyte according to claim 3, it is characterised in that: the step (1) in, heating time 2-100h.
9. a kind of preparation method of lithium ion solid electrolyte according to claim 3, it is characterised in that: the step (2) it in, when being cleaned, is cleaned using methanol, ethyl alcohol or deionized water.
10. a kind of preparation method of lithium ion solid electrolyte according to claim 3, it is characterised in that: the step Suddenly in (3), heat treatment temperature be 300-900 DEG C, preferably 300-700 DEG C, heat treatment time 2-10h.
CN201910562448.5A 2019-06-26 2019-06-26 Lithium ion solid electrolyte and preparation method thereof Pending CN110212240A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111446494A (en) * 2020-04-17 2020-07-24 上海空间电源研究所 Glass state lithium ion solid electrolyte and preparation method thereof
WO2020258803A1 (en) * 2019-06-26 2020-12-30 上海空间电源研究所 Lithium-ion solid electrolyte and preparation method therefor
CN112397774A (en) * 2020-10-19 2021-02-23 上海空间电源研究所 Solid electrolyte membrane, preparation method and solid battery

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101811828A (en) * 2009-02-23 2010-08-25 中国科学院上海硅酸盐研究所 NASICON structure glass ceramic sodion solid electrolytes and preparation method thereof
CN103332864A (en) * 2013-06-07 2013-10-02 宁波大学 Superionic-conductor-containing sulfur glass ceramic material and preparation method thereof
CN104583144A (en) * 2012-08-31 2015-04-29 旭硝子株式会社 Method for manufacturing lithium-ion-conducting glass ceramic
US20160329598A1 (en) * 2014-01-22 2016-11-10 Schott Ag Ion-conducting glass ceramic having garnet-like crystal structure
CN107305965A (en) * 2016-04-25 2017-10-31 松下知识产权经营株式会社 Battery and cell manufacturing method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101811828A (en) * 2009-02-23 2010-08-25 中国科学院上海硅酸盐研究所 NASICON structure glass ceramic sodion solid electrolytes and preparation method thereof
CN104583144A (en) * 2012-08-31 2015-04-29 旭硝子株式会社 Method for manufacturing lithium-ion-conducting glass ceramic
CN103332864A (en) * 2013-06-07 2013-10-02 宁波大学 Superionic-conductor-containing sulfur glass ceramic material and preparation method thereof
US20160329598A1 (en) * 2014-01-22 2016-11-10 Schott Ag Ion-conducting glass ceramic having garnet-like crystal structure
CN107305965A (en) * 2016-04-25 2017-10-31 松下知识产权经营株式会社 Battery and cell manufacturing method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020258803A1 (en) * 2019-06-26 2020-12-30 上海空间电源研究所 Lithium-ion solid electrolyte and preparation method therefor
CN111446494A (en) * 2020-04-17 2020-07-24 上海空间电源研究所 Glass state lithium ion solid electrolyte and preparation method thereof
CN112397774A (en) * 2020-10-19 2021-02-23 上海空间电源研究所 Solid electrolyte membrane, preparation method and solid battery

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Application publication date: 20190906