CN114744285A - Solid electrolyte suitable for lithium ion battery and preparation method and application thereof - Google Patents

Solid electrolyte suitable for lithium ion battery and preparation method and application thereof Download PDF

Info

Publication number
CN114744285A
CN114744285A CN202210506226.3A CN202210506226A CN114744285A CN 114744285 A CN114744285 A CN 114744285A CN 202210506226 A CN202210506226 A CN 202210506226A CN 114744285 A CN114744285 A CN 114744285A
Authority
CN
China
Prior art keywords
solid electrolyte
latp
lithium ion
ion battery
llzo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210506226.3A
Other languages
Chinese (zh)
Inventor
李旺
周兰
廖文俊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Electric Group Corp
Original Assignee
Shanghai Electric Group Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Electric Group Corp filed Critical Shanghai Electric Group Corp
Priority to CN202210506226.3A priority Critical patent/CN114744285A/en
Publication of CN114744285A publication Critical patent/CN114744285A/en
Pending legal-status Critical Current

Links

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
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a solid electrolyte suitable for a lithium ion battery and a preparation method and application thereof. The preparation method comprises the following steps: step S1: dispersing a polymer and a lithium salt in an organic solvent, adding a LATP-based or LLZO-based solid electrolyte, and stirring until the solution is uniformly mixed to obtain a mixed solution; step S2: and ball-milling the mixed solution by using a ball mill, and spray-drying and evaporating to dryness to obtain the LATP-based solid electrolyte or LLZO-based solid electrolyte coated by the polymer electrolyte. According to the invention, the LATP-based/LLZO-based solid electrolyte is coated by the polymer electrolyte, so that the stability of the LATP-based/LLZO-based solid electrolyte to air is improved, and the stability of the LATP-based solid electrolyte to metal lithium is also improved.

Description

Solid electrolyte suitable for lithium ion battery and preparation method and application thereof
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a solid electrolyte suitable for a lithium ion battery and a preparation method and application thereof.
Background
Lithium ion batteries are the most widely used commercial energy storage systems because of their advantages of high energy density, high operating voltage, no memory effect, long cycle life, and environmental friendliness. Although the traditional liquid lithium ion battery has good ionic conductivity and wettability, the traditional liquid lithium ion battery also has the safety problems of poor thermal stability, flammability, easy liquid leakage and the like.
A solid electrolyte having a higher energy density and excellent safety performance becomes a potentially best approach to solve the above-described problems instead of a liquid electrolyte. The following studies were performed by those skilled in the art:
patent CN111559740A adopts a template method to prepare LATP (lithium aluminum titanium phosphate) with space gaps, and the interaction between LATP and lithium metal is relieved through the gap structure, so that the stability of LATP to lithium metal can be relieved to a certain extent. However, the LATP is less dense due to the presence of the interstitial spaces, which is detrimental to the application of LATP, and the method does not alter the direct contact of LATP with lithium metal.
Patent CN110265709A uses amorphous glassy solid electrolyte pair LLZTO (Li)6.4La3Zr1.4Ta0.6O12) High-temperature coating is carried out, so that the stability of the LLZTO to the anode and cathode materials is improved. However, the coating needs to be carried out at low pressure and high temperature, so that the requirement on equipment is high and the energy consumption is high.
Patent CN110176628A adopts zirconium dioxide coating and LATP metal oxide to carry out high-temperature coating on LLZTO, thus improving the stability of LLZTO to air. However, after the material is coated, two times of high-temperature sintering are needed, so that the energy consumption is large, the method is not economical, and the large-scale commercial popularization is difficult.
In view of the above-mentioned drawbacks of the prior art, the present invention provides a solid electrolyte for lithium ion batteries.
Disclosure of Invention
The invention provides a solid electrolyte suitable for a lithium ion battery, which has simple and controllable preparation process and improves the stability of LATP-based/LLZO (lithium lanthanum zirconium oxygen) based solid electrolyte.
In a first aspect, the present invention provides a method for preparing a solid electrolyte suitable for use in a lithium ion battery, comprising the steps of:
step S1: dispersing a polymer and a lithium salt in an organic solvent, adding a LATP-based or LLZO-based solid electrolyte, and stirring until the solution is uniformly mixed to obtain a mixed solution;
step S2: and ball-milling the mixed solution, and spray-drying and evaporating to dryness to obtain the LATP-based solid electrolyte or LLZO-based solid electrolyte coated by the polymer electrolyte.
Preferably, the polymer is PAA (polyacrylic acid).
Preferably, the lithium salt is LiTFSI (lithium bis (trifluoromethanesulfonylimide)).
Preferably, the organic solvent is NMP (N-methylpyrrolidone).
Preferably, the molecular weight of the polymer is 10000-200000.
Preferably, the molar ratio of the lithium ions in the polymer and the lithium salt is 1: 100-200.
Preferably, the mass ratio of the lithium salt to the organic solvent is 1: 150-500.
Preferably, the mass ratio of the LATP-based solid electrolyte or the LLZO-based solid electrolyte to the organic solvent is 1: 5-10.
Preferably, the ball milling time is 1-2 h.
In a second aspect, the present invention provides a solid electrolyte suitable for use in a lithium ion battery, prepared by the above method.
In a third aspect, the present invention provides a lithium ion battery, which uses the above solid electrolyte suitable for a lithium ion battery.
By adopting the technical scheme, compared with the prior art, the invention has the following technical effects:
(1) the LATP-based/LLZO-based electrolyte is coated by ball-milling, depolymerizing and drying the polymer dispersed in an organic solvent such as NMP, so as to realize uniform coating of small particles.
(2) The coating of the LATP-based/LLZO-based solid electrolyte with the polymer electrolyte improves the stability of the LATP-based/LLZO-based solid electrolyte to air and improves the stability of the LATP-based electrolyte to metallic lithium.
(3) The coating of the polymer electrolyte can improve the flexibility of the LATP-based electrolyte and the LLZO-based electrolyte, and is beneficial to processing and forming.
(4) The method provided by the invention is simple and controllable, only involves mixing, depolymerization and drying in the related procedures, does not involve a sintering process with high energy consumption, and is easy for large-scale popularization.
Detailed Description
In a first aspect, the present invention provides a method for preparing a solid electrolyte suitable for use in a lithium ion battery, comprising the steps of:
step S1: dispersing a polymer and lithium salt in an organic solvent, adding a LATP-based or LLZO-based solid electrolyte, and stirring until the solution is uniformly mixed to obtain a mixed solution;
step S2: and ball-milling the mixed solution by using a ball mill, and spray-drying and evaporating to dryness to obtain the LATP-based solid electrolyte or LLZO-based solid electrolyte coated by the polymer electrolyte.
In a second aspect, the invention provides a solid electrolyte suitable for a lithium ion battery, which is prepared by the method.
In a third aspect, the present invention provides a lithium ion battery, which adopts the above solid electrolyte suitable for lithium ion batteries.
The present invention will now be described in detail and specifically by the following examples to provide a better understanding of the present invention, but the following examples are not intended to limit the scope of the present invention.
Example 1
The embodiment provides a solid electrolyte suitable for a lithium ion battery, and a specific preparation method of the solid electrolyte comprises the following steps:
step S1: adding 5g of PAN (Mw: 150000) and 1.35g of LiTFSI into 215g of NMP, stirring for 10min, adding 35g of LATP-based solid electrolyte into the mixed solution, and stirring for 10min until the solution is uniformly mixed;
step S2: and ball-milling the mixed solution by using a ball mill for 1h, and then spray-drying and evaporating to dryness to obtain the PAN-coated LATP-based solid electrolyte (marked as LATP/PAN).
Example 2
The embodiment provides a solid electrolyte suitable for a lithium ion battery, and a specific preparation method of the solid electrolyte comprises the following steps:
step S1: adding 5g of PAN (Mw: 150000) and 1.35g of LiTFSI into 215g of NMP, stirring for 10min, adding 30g of LLZO-based solid electrolyte into the mixed solution, and stirring for 10min until the solution is uniformly mixed;
step S2: and (3) performing ball milling on the mixed solution for 1h by using a ball mill, and performing spray drying and evaporation to obtain the PAN-coated LLZO-based solid electrolyte (marked as LLZO/PAN).
Comparative example 1
The present comparative example provides a LATP solid electrolyte without any treatment.
Comparative example 2
This comparative example provides a LLZO solid electrolyte without any treatment.
Test example 1
The solid electrolytes prepared in example 1 and comparative example 1 were subjected to stability test by the following specific test procedures:
after the material is placed in the air for 300 days, the cold press molding technology is adopted, the material is subjected to tabletting treatment, silver colloid is coated to prepare a blocking electrode, and the room-temperature conductivity is tested;
forming a symmetrical battery with a metal lithium sheet at 0.05mA/cm2Constant current test was performed.
The test results are shown in table 1 below:
TABLE 1 LATP-based solid electrolyte stability contrast
Figure BDA0003622503390000041
According to the above table, compared with the LATP solid electrolyte which is not treated, the PAN-coated LATP-based solid electrolyte prepared by the method provided by the invention has the ion conductivity which is much higher than that of the LATP solid electrolyte after being placed for 300 days, i.e. the stability of the PAN-coated LATP-based solid electrolyte prepared by the method provided by the invention to air is greatly improved; the LATP-based solid electrolyte and a metal lithium sheet form a symmetrical battery, and a constant current test is carried out at a current density of 0.05mA/cm2, wherein the LATP-based solid electrolyte can still stably run after 150 hours, namely the stability of the LATP-based solid electrolyte coated by the PAN prepared by the method is greatly improved.
Test example 2
The solid electrolytes prepared in example 2 and comparative example 2 were subjected to stability test by the following specific test procedures:
after the material is placed in the air for 200 days, the cold press molding technology is adopted, the material is subjected to tabletting treatment, silver colloid is smeared to prepare a blocking electrode, and the room-temperature conductivity is tested.
The test results are shown in table 2 below:
TABLE 2 LLZO-based solid electrolyte stability contrast
Figure BDA0003622503390000051
According to the above table, compared with the LLZO solid electrolyte without any treatment, the PAN-coated LLZO solid electrolyte prepared by the method provided by the present invention has a much higher ionic conductivity than the LLZO solid electrolyte without any treatment after standing for 200 days, i.e., the stability of the PAN-coated LLZO solid electrolyte prepared by the method of the present invention to air is greatly improved.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.

Claims (10)

1. A preparation method of a solid electrolyte suitable for a lithium ion battery is characterized by comprising the following steps:
step S1: dispersing a polymer and a lithium salt in an organic solvent, adding a LATP-based or LLZO-based solid electrolyte, and stirring until the solution is uniformly mixed to obtain a mixed solution;
step S2: and ball-milling the mixed solution, and spray-drying and evaporating to dryness to obtain the LATP-based solid electrolyte or LLZO-based solid electrolyte coated by the polymer electrolyte.
2. The method of claim 1, wherein the polymer is PAA.
3. The method of claim 1, wherein the lithium salt is LiTFSI.
4. The method of claim 1, wherein the organic solvent is NMP.
5. The method for preparing the solid electrolyte of the lithium ion battery according to claim 1, wherein the molecular weight of the polymer is 10000-200000.
6. The method of claim 1, wherein the molar ratio of the polymer to the lithium ions in the lithium salt is 1:100 to 200.
7. The method for preparing the solid electrolyte of the lithium ion battery according to claim 1, wherein the mass ratio of the lithium salt to the organic solvent is 1: 150-500.
8. The method according to claim 1, wherein the LATP-based solid electrolyte or the LLZO-based solid electrolyte is present in a mass ratio of 1:5 to 10 relative to the organic solvent.
9. A solid electrolyte suitable for use in a lithium ion battery, prepared by the method of any one of claims 1 to 8.
10. A lithium ion battery using a solid state electrolyte suitable for use in a lithium ion battery as claimed in claim 9.
CN202210506226.3A 2022-04-28 2022-04-28 Solid electrolyte suitable for lithium ion battery and preparation method and application thereof Pending CN114744285A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210506226.3A CN114744285A (en) 2022-04-28 2022-04-28 Solid electrolyte suitable for lithium ion battery and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210506226.3A CN114744285A (en) 2022-04-28 2022-04-28 Solid electrolyte suitable for lithium ion battery and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN114744285A true CN114744285A (en) 2022-07-12

Family

ID=82286216

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210506226.3A Pending CN114744285A (en) 2022-04-28 2022-04-28 Solid electrolyte suitable for lithium ion battery and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114744285A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117174988A (en) * 2023-09-01 2023-12-05 哈尔滨工业大学 Preparation method of lithium/sodium ion battery material and application of lithium/sodium ion battery material in lithium/sodium ion battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117174988A (en) * 2023-09-01 2023-12-05 哈尔滨工业大学 Preparation method of lithium/sodium ion battery material and application of lithium/sodium ion battery material in lithium/sodium ion battery
CN117174988B (en) * 2023-09-01 2024-04-30 哈尔滨工业大学 Preparation method of lithium/sodium ion battery material and application of lithium/sodium ion battery material in lithium/sodium ion battery

Similar Documents

Publication Publication Date Title
Wang et al. Composite polymer electrolyte with three-dimensional ion transport channels constructed by NaCl template for solid-state lithium metal batteries
CN108963235B (en) Graphene-enhanced carbon-coated titanium manganese phosphate sodium microsphere electrode material and preparation method and application thereof
CN109671985A (en) A kind of application of integral structure in solid lithium ion battery
CN106159318A (en) Novel slice type solid-state serondary lithium battery that garnet-type solid electrolyte supports and preparation method thereof
CN109904387B (en) Preparation method of high-performance lithium battery positive plate
CN104617256A (en) Nano-zinc oxide-graphite-graphene composite material as well as preparation method and application thereof
CN112038614B (en) Negative electrode material for sodium ion battery and preparation method thereof
CN108110324A (en) A kind of preparation method of solid lithium ion battery
CN109728342A (en) A kind of selfreparing composite solid electrolyte, quasi-solid electrolyte and lithium battery
CN103972466A (en) Positive electrode of high temperature lithium thionyl chloride battery and preparation method thereof
CN104393275A (en) Preparation method of carbon-coated lithium titanate battery material
CN112018392A (en) Preparation method of lithium ion battery cathode taking PEO-based polymer electrolyte as adhesive
CN114744285A (en) Solid electrolyte suitable for lithium ion battery and preparation method and application thereof
CN107482184A (en) A kind of preparation method of lithium titanate cathode of lithium ion battery composite
CN106981639B (en) Preparation method of organic salt coated lithium iron phosphate cathode material
WO2023241054A1 (en) Lithium-salt-free composite solid electrolyte membrane and preparation method therefor
CN107146881B (en) Modified Nickel lithium manganate cathode composite material and preparation method, lithium ion battery
CN114243098B (en) Composite solid electrolyte and preparation method and application thereof
CN105226251A (en) A kind of pure carbon compound cathode materials and preparation method thereof
CN113224378B (en) Lithium battery, solid electrolyte, and preparation method and application thereof
CN114744291A (en) High-voltage-resistant composite solid electrolyte, preparation method thereof and all-solid-state lithium battery
CN108461740A (en) A kind of LiVOPO4Nickelic tertiary cathode material of lithium ion battery of cladding and its preparation method and application
CN107565155B (en) Lithium ion battery
CN115275362B (en) Solid electrolyte containing heterogeneous ionic gel buffer layer and preparation and application thereof
CN114613545B (en) Preparation method of composite conductive paste with excellent electrical properties

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination