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CN106129465A - Fluorine-doped lithium ion solid electrolyte and preparation method thereof - Google Patents

Fluorine-doped lithium ion solid electrolyte and preparation method thereof Download PDF

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Publication number
CN106129465A
CN106129465A CN201610653765.4A CN201610653765A CN106129465A CN 106129465 A CN106129465 A CN 106129465A CN 201610653765 A CN201610653765 A CN 201610653765A CN 106129465 A CN106129465 A CN 106129465A
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solid electrolyte
lithium ion
ion solid
doped lithium
preparation
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CN106129465B (en
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李文龙
张洪
刘欢
王红飞
杨利青
王浩静
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XiAn Institute of Optics and Precision Mechanics of CAS
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XiAn Institute of Optics and Precision Mechanics of CAS
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561Accumulators 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
    • H01M10/0562Solid materials
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy 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)
  • Conductive Materials (AREA)
  • Secondary Cells (AREA)

Abstract

The invention belongs to the field of lithium ion electrolyte manufacture, and particularly relates to a fluorine-doped lithium ion solid electrolyte and a preparation method thereof, wherein the stoichiometric formula of the lithium ion solid electrolyte is Li10+x‑yM1+ xP2‑xS12‑yFyWherein: x is 0.1 to 1.0, y is 0.1 to 0.3, and M is Ge, Si or Sn. Li prepared by the invention10+x‑yM1+xP2‑ xS12‑yFyLithium ion solid electrolyte using part FSubstituted S2‑Form P-F4The bond energy of the P-F covalent bond is larger than that of the P-S covalent bond, the strengthening of the P-F bond weakens the constraint of fluorine ions on lithium ions, and the migration speed of the lithium ions is improved. So that Li10+x‑yM1+ xP2‑xS12‑yFyThe lithium ion conductivity of the lithium ion solid electrolyte reaches 2.0 multiplied by 10‑2S/cm and above.

Description

A kind of fluorine doped lithium ion solid electrolyte and preparation method thereof
Technical field
The invention belongs to lithium-ion electrolyte and manufacture field, be specifically related to a kind of fluorine doped lithium ion solid electrolyte and system thereof Preparation Method.
Background technology
The increase developing the usage amount to the energy and exhaustion, the people day by day of non-renewable resources along with industrial society More and more urgent to the demand of new forms of energy, the requirement to energy storage technology is more and more stricter.Society, lithium ion battery is one Planting crucial energy-storage system, they can serve as depositing of hybrid vehicle, pure electric automobile or even wind and solar energy homenergic Reservoir.Automobile power cell is higher to the requirement of lithium ion battery, and it is relatively low that major requirement battery material has price, security performance Preferably, energy density is higher, and charge-discharge magnification performance is good, service life the feature such as length.But, lithium-ion electric in the market Pond, is mostly the lithium ion battery using liquid electrolyte, and the lithium salts of liquid electrolyte is dissolved in the middle of organic solution, and comprises Multiple functional additive, the lithium salts that liquid electrolyte is conventional is LiPF6With LiFSI etc.;Organic solvent mostly is cyclic carbonate (EC, PC), linear carbonate (DEC, EDC and DMC etc.) and carboxylic acid esters (MF, MA and EA etc.).Lithium ion containing electrolyte Battery in use can also exist potential safety hazard, such as: inflammable, explosive, perishable etc., frequent electronic vapour in society Car spontaneous combustion, the security incident such as battery of mobile phone blast causes mainly due to the electrolyte in lithium ion battery.
In order to solve the safety problem of lithium ion battery, current electrolysis liquid develops towards solid state direction, at solid state electrolysis During matter substitutes organic liquid electrolyte, the energy density of conventional lithium ion battery is on the low side and the shortest the two in service life Key issue is expected to be improved, and this also complies with the developing direction of following energy storage power supply.But the solid electrolyte of report at present There is the problem that lithium ion conductivity is too low to realize commercial applications.
Summary of the invention
The technical problem the lowest in order to solve lithium ion conductivity, the present invention provides one to mix F lithium ion solid electrolyte And preparation method thereof.
The technical solution of the present invention is: a kind of fluorine doped lithium ion solid electrolyte, it is characterized in that described lithium The stoichiometric equation of ion solid electrolyte is Li10+x-yM1+xP2-xS12-yFy, wherein: x=0.1~1.0, y=0.1~0.3, M For Ge, Si or Sn.
The stoichiometric equation of above-mentioned lithium ion solid electrolyte is Li9.7+xM1+xP2-xS11.7F0.3, wherein: x=0.1~ 1.0.This lithium ion solid electrolyte has the most higher lithium ion conductivity.
The present invention also provides for a kind of fluorine doped lithium ion solid electrolyte preparation method, its be characterized in that include following Step:
1] by raw material Li2S、MS2、P2S5With LiF according to 4.75~5.40:1.1~2.0:0.5~0.95:0.1~0.3 Mol ratio mixes;Wherein, M is Ge, Si or Sn;
2] mixed raw material ball milling under inert atmosphere protection is become uniformed powder;
3] powder body after ball milling is pressed into electrolyte sheet;
4] electrolyte sheet is sintered under inert atmosphere protection the solid electrolyte sheet of densification.
The beneficial effects of the present invention is: the Li prepared by the present invention10+x-yM1+xP2-xS12-yFyLithium ion solid electrolyte Use part F-Replace S2-, form P-F4Covalent bond, the bond energy of P-F covalent bond is more than the bond energy of P-S covalent bond, adding of P-F key Weaken by force the fluorion constraint to lithium ion, improve the migration velocity of lithium ion.Make Li10+x-yM1+xP2-xS12-yFyLithium from The lithium ion conductivity of sub-solid electrolyte has reached 2.0 × 10-2S/cm and more than.
Accompanying drawing explanation
Fig. 1 is the exchange resistance under electrochemical workstation of the lithium ion solid electrolyte thin slice of the embodiment of the present invention 1 preparation Anti-figure;
Fig. 2 is the exchange resistance under electrochemical workstation of the lithium ion solid electrolyte thin slice of the embodiment of the present invention 2 preparation Anti-figure;
Fig. 3 is the exchange resistance under electrochemical workstation of the lithium ion solid electrolyte thin slice of the embodiment of the present invention 3 preparation Anti-figure;
Fig. 4 is the exchange resistance under electrochemical workstation of the lithium ion solid electrolyte thin slice of the embodiment of the present invention 4 preparation Anti-figure;
Fig. 5 is the exchange resistance under electrochemical workstation of the lithium ion solid electrolyte thin slice of the embodiment of the present invention 5 preparation Anti-figure;
Fig. 6 is the exchange resistance under electrochemical workstation of the lithium ion solid electrolyte thin slice of the embodiment of the present invention 6 preparation Anti-figure;
Fig. 7 is the exchange resistance under electrochemical workstation of the lithium ion solid electrolyte thin slice of the embodiment of the present invention 7 preparation Anti-figure.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is described in detail.
Embodiment 1: in this technical scheme, by Li2S:GeS2: P2S5: LiF according to 4.95:1.1:0.95:0.1 (mole Than) ratio uniform mixing, the raw material mixed is put in ball grinder, under the protection of argon gas atmosphere, with 500 revs/min Rotating speed ball milling 10 hours, the powder body after being terminated by ball milling depresses to electrolyte sheet at the pressure of 200Mpa, by electrolyte thin Sheet is placed in vacuum atmosphere tube furnace, under an argon atmosphere with the ramp to 600 DEG C of 2 DEG C/min, is incubated at 600 DEG C 10h sinters the solid electrolyte sample strip of densification into.If Fig. 1 is to consist of Li10Ge1.1P1.9S11.9F0.1, solid electrolyte sheet AC impedance figure under electrochemical workstation, calculating electrical conductivity from figure is 2.3 × 10-2S/cm。
Embodiment 2: by Li2S:SnS2: P2S5: LiF mixes according to the ratio uniform of 4.85:1.1:0.95:0.2 (mol ratio) Closing, put in ball grinder by the raw material mixed, under the protection of argon gas atmosphere, the rotating speed ball milling 24 with 350 revs/min is little Time, the powder body after being terminated by ball milling depresses to electrolyte sheet at the pressure of 150Mpa, electrolyte sheet is placed in vacuum atmosphere In tube furnace, under an argon atmosphere with the ramp to 650 DEG C of 3 DEG C/min, at 650 DEG C, it is incubated 8h sinters densification into Solid electrolyte sample strip.If Fig. 2 is to consist of Li9.9Sn1.1P1.9S11.8F0.2, solid electrolyte sheet is at electrochemical workstation Lower AC impedance figure, calculating electrical conductivity from figure is 2.8 × 10-2S/cm。
Embodiment 3: by Li2S:SiS2: P2S5: LiF mixes according to the ratio uniform of 4.75:1.1:0.95:0.3 (mol ratio) Closing, put in ball grinder by the raw material mixed, under the protection of argon gas atmosphere, the rotating speed ball milling 25 with 300 revs/min is little Time, the powder body after being terminated by ball milling depresses to electrolyte sheet at the pressure of 100Mpa, electrolyte sheet is placed in vacuum atmosphere In tube furnace, under an argon atmosphere with the ramp to 550 DEG C of 2 DEG C/min, at 550 DEG C, it is incubated 30h sinters densification into Solid electrolyte sample strip.If Fig. 3 is to consist of Li9.8Si1.1P1.9S11.7F0.3, solid electrolyte sheet is at electrochemical workstation Lower AC impedance figure, calculating electrical conductivity from figure is 2.9 × 10-2S/cm。
Embodiment 4: by Li2S:GeS2: P2S5: LiF mixes according to the ratio uniform of 5.05:1.3:0.85:0.1 (mol ratio) Closing, put in ball grinder by the raw material mixed, under the protection of argon gas atmosphere, the rotating speed ball milling 20 with 300 revs/min is little Time, the powder body after being terminated by ball milling depresses to electrolyte sheet at the pressure of 200Mpa, electrolyte sheet is placed in vacuum atmosphere In tube furnace, under an argon atmosphere with the ramp to 600 DEG C of 3 DEG C/min, at 600 DEG C, it is incubated 20h sinters densification into Solid electrolyte sample strip.If Fig. 4 is to consist of Li10.2Ge1.3P1.7S11.9F0.1, solid electrolyte sheet is at electrochemical workstation Lower AC impedance figure, calculating electrical conductivity from figure is 2.4 × 10-2S/cm。
Embodiment 5: by Li2S:SiS2: P2S5: LiF mixes according to the ratio uniform of 4.95:1.5:0.75:0.3 (mol ratio) Closing, put in ball grinder by the raw material mixed, under the protection of argon gas atmosphere, the rotating speed ball milling 10 with 500 revs/min is little Time, the powder body after being terminated by ball milling depresses to electrolyte sheet at the pressure of 200Mpa, electrolyte sheet is placed in vacuum atmosphere In tube furnace, under an argon atmosphere with the ramp to 650 DEG C of 3 DEG C/min, at 650 DEG C, it is incubated 20h sinters densification into Solid electrolyte sample strip.If Fig. 5 is to consist of Li10.2Si1.5P1.5S11.7F0.3, solid electrolyte sheet is at electrochemical workstation Lower AC impedance figure, calculating electrical conductivity from figure is 3.5 × 10-2S/cm。
Embodiment 6: by Li2S:SnS2: P2S5: LiF mixes according to the ratio uniform of 5.15:1.7:0.65:0.2 (mol ratio) Closing, put in ball grinder by the raw material mixed, under the protection of argon gas atmosphere, the rotating speed ball milling 15 with 400 revs/min is little Time, the powder body after being terminated by ball milling depresses to electrolyte sheet at the pressure of 150Mpa, electrolyte sheet is placed in vacuum atmosphere In tube furnace, under an argon atmosphere with the ramp to 600 DEG C of 2 DEG C/min, at 600 DEG C, it is incubated 15h sinters densification into Solid electrolyte sample strip.If Fig. 6 is to consist of Li10.5Sn1.7P1.3S11.8F0.2, solid electrolyte sheet is at electrochemical workstation Lower AC impedance figure, calculating electrical conductivity from figure is 3.1 × 10-2S/cm。
Embodiment 7: by Li2S:SiS2: P2S5: LiF mixes according to the ratio uniform of 5.4:2.0:0.5:0.1 (mol ratio), The raw material mixed is put in ball grinder, under the protection of argon gas atmosphere, with the rotating speed ball milling 20 hours of 300 revs/min, will Powder body after ball milling terminates depresses to electrolyte sheet at the pressure of 200Mpa, and electrolyte sheet is placed in vacuum atmosphere tube furnace In, under an argon atmosphere with the ramp to 550 DEG C of 3 DEG C/min, at 550 DEG C, it is incubated 30h sinters the solid-state electricity of densification into Solve quality sample sheet.If Fig. 7 is to consist of Li10.9Si2P1S11.9F0.1, solid electrolyte sheet exchanges resistance under electrochemical workstation Anti-figure, calculating electrical conductivity from figure is 2.0 × 10-2S/cm。

Claims (7)

1. a fluorine doped lithium ion solid electrolyte, it is characterised in that: the stoichiometric equation of described lithium ion solid electrolyte is Li10+x-yM1+xP2-xS12-yFy, wherein: x=0.1~1.0, y=0.1~0.3, M is Ge, Si or Sn.
Fluorine doped lithium ion solid electrolyte the most according to claim 1, it is characterised in that: described lithium ion solid electrolyte Stoichiometric equation be Li9.7+xM1+xP2-xS11.7F0.3, wherein: x=0.1~1.0.
3. a fluorine doped lithium ion solid electrolyte preparation method, it is characterised in that: comprise the following steps:
1] by raw material Li2S、MS2、P2S5With LiF according to 4.75~5.40:1.1~2.0:0.5~0.95:0.1~0.3 mole Ratio mixes;Wherein, M is Ge, Si or Sn;
2] mixed raw material ball milling under inert atmosphere protection is become uniformed powder;
3] powder body after ball milling is pressed into electrolyte sheet;
4] electrolyte sheet is sintered under inert atmosphere protection the solid electrolyte sheet of densification.
Fluorine doped lithium ion solid electrolyte preparation method the most according to claim 3, it is characterised in that: described step 2] in Ball milling speed be 200~500 revs/min, Ball-milling Time is 5~30 hours.
Fluorine doped lithium ion solid electrolyte preparation method the most according to claim 4, it is characterised in that: described step 3] in Pressing pressure be 50~200MPa.
Fluorine doped lithium ion solid electrolyte preparation method the most according to claim 5, it is characterised in that: described step 4] in Sintering step include electrolyte sheet under an inert atmosphere with the ramp of 1~3 DEG C/min to 500 DEG C~650 DEG C, It is incubated 8h~30h at 500 DEG C~650 DEG C and sinters the solid electrolyte sheet of densification into.
7. according to described fluorine doped lithium ion solid electrolyte preparation method arbitrary in claim 3-6, it is characterised in that: described Inert atmosphere is argon gas atmosphere.
CN201610653765.4A 2016-08-10 2016-08-10 Fluorine-doped lithium ion solid electrolyte and preparation method thereof Expired - Fee Related CN106129465B (en)

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Cited By (7)

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CN106972195A (en) * 2017-04-17 2017-07-21 哈尔滨工业大学无锡新材料研究院 A kind of inorganic sulphide electrolyte and preparation method thereof
CN108091923A (en) * 2016-11-22 2018-05-29 东莞新能源科技有限公司 Solid electrolyte and preparation method thereof and all solid lithium secondary battery
CN108511795A (en) * 2018-04-02 2018-09-07 西安电子科技大学 A kind of O2-And F-Cooperate with the LISICON type solid electrolyte materials and preparation method thereof of doping
CN109638360A (en) * 2018-11-09 2019-04-16 哈尔滨工业大学无锡新材料研究院 A kind of preparation method of all solid state lithium-sulfur cell and prepare mold
CN111900461A (en) * 2020-07-17 2020-11-06 国联汽车动力电池研究院有限责任公司 Fluorine-containing solid electrolyte for high-voltage all-solid-state battery and preparation method and application thereof
JPWO2019239949A1 (en) * 2018-06-13 2021-07-08 三菱瓦斯化学株式会社 LGPS system solid electrolyte and manufacturing method
US20220077463A1 (en) * 2018-11-22 2022-03-10 Nippon Chemi-Con Corporation Metal compound particle group, electrode for power storage device, power storage device, and method for producing metal compound particle group

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CN104011268A (en) * 2011-11-02 2014-08-27 I-Ten公司 Method for preparing compact film by electrophoresis technology
CN104604013A (en) * 2012-09-11 2015-05-06 丰田自动车株式会社 Sulfide solid electrolyte
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CN108091923A (en) * 2016-11-22 2018-05-29 东莞新能源科技有限公司 Solid electrolyte and preparation method thereof and all solid lithium secondary battery
CN106972195A (en) * 2017-04-17 2017-07-21 哈尔滨工业大学无锡新材料研究院 A kind of inorganic sulphide electrolyte and preparation method thereof
CN108511795A (en) * 2018-04-02 2018-09-07 西安电子科技大学 A kind of O2-And F-Cooperate with the LISICON type solid electrolyte materials and preparation method thereof of doping
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JPWO2019239949A1 (en) * 2018-06-13 2021-07-08 三菱瓦斯化学株式会社 LGPS system solid electrolyte and manufacturing method
JP7294334B2 (en) 2018-06-13 2023-06-20 三菱瓦斯化学株式会社 LGPS-based solid electrolyte and manufacturing method
CN109638360A (en) * 2018-11-09 2019-04-16 哈尔滨工业大学无锡新材料研究院 A kind of preparation method of all solid state lithium-sulfur cell and prepare mold
CN109638360B (en) * 2018-11-09 2022-03-08 哈尔滨工业大学无锡新材料研究院 Preparation method and preparation mold of all-solid-state lithium-sulfur battery
US20220077463A1 (en) * 2018-11-22 2022-03-10 Nippon Chemi-Con Corporation Metal compound particle group, electrode for power storage device, power storage device, and method for producing metal compound particle group
CN111900461A (en) * 2020-07-17 2020-11-06 国联汽车动力电池研究院有限责任公司 Fluorine-containing solid electrolyte for high-voltage all-solid-state battery and preparation method and application thereof
CN111900461B (en) * 2020-07-17 2022-06-28 国联汽车动力电池研究院有限责任公司 Fluorine-containing solid electrolyte for high-voltage all-solid-state battery and preparation method and application thereof

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