CN113851700A - Preparation method of lithium germanium phosphorus sulfur for all-solid-state battery material - Google Patents
Preparation method of lithium germanium phosphorus sulfur for all-solid-state battery material Download PDFInfo
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- CN113851700A CN113851700A CN202111126248.9A CN202111126248A CN113851700A CN 113851700 A CN113851700 A CN 113851700A CN 202111126248 A CN202111126248 A CN 202111126248A CN 113851700 A CN113851700 A CN 113851700A
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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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
- H01M10/058—Construction or manufacture
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- 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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- 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
Abstract
The invention discloses a preparation method of lithium germanium phosphorus sulfur for an all-solid-state battery material, which specifically comprises the following steps: (1) mixing a lithium compound, a germanium compound and a phosphorus compound, tabletting, carrying out heat treatment, cooling and then carrying out ball milling to obtain a sulfur-based solid electrolyte; (2) uniformly mixing resin and lithium salt to obtain an organic solid electrolyte; (3) uniformly mixing the sulfur-based solid electrolyte and the organic solid electrolyte to obtain a base material; (4) and adding the base material into the impregnation liquid for impregnation, and then drying and curing under a vacuum condition to obtain the coating. The sulfur-based solid electrolyte and the organic solid electrolyte are combined to prepare the composite solid electrolyte, so that the advantages of the sulfur-based solid electrolyte and the organic solid electrolyte can be effectively combined to form the solid electrolyte with good lithium ion conductivity, electrochemical stability and mechanical property.
Description
Technical Field
The invention relates to the technical field of all-solid-state batteries, in particular to a preparation method of a lithium germanium phosphorus sulfur material for all-solid-state batteries.
Background
All-solid-state batteries are an advanced battery technology. Unlike lithium ion batteries and lithium ion polymer batteries that are currently in widespread use, an all-solid-state battery is a battery that uses a solid electrode and a solid electrolyte. Because its electrolyte is solid-state, density and structure that have can let more charged ions gather in one end, conduct bigger electric current, and then promote battery capacity, consequently, same electric quantity, all-solid-state battery volume will become littleer. Moreover, because of no electrolyte in the all-solid-state battery, the sealing is easier, and when the battery is used on large-scale equipment such as automobiles, cooling pipes, electronic controls and the like do not need to be additionally arranged, so that the cost is saved, and the weight can be effectively reduced.
Since the scientific community considers that lithium ion batteries have reached the limit, all-solid-state batteries have been regarded in recent years as batteries that can inherit the position of lithium ion batteries.
Sulfur-based solid electrolytes have high ionic conductivity and a wide electrochemical window, and are considered to be one of the most promising solid electrolytes. However, the sulfide solid electrolyte reacts with the interface of the metallic lithium negative electrode, so that the sulfur-based solid electrolyte is decomposed, the interface resistance of the electrolyte and the metallic lithium is increased, and the electrochemical cycle performance of the solid battery is affected. The organic solid electrolyte has good film-forming properties and flexibility, but its ionic conductivity at room temperature is low.
Therefore, how to combine the advantages of the sulfur-based solid electrolyte and the organic solid electrolyte to prepare the composite solid electrolyte is a problem that needs to be solved urgently by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing lithium germanium phosphorus sulfur for an all-solid-state battery material, wherein the solid-state electrolyte has good ionic conductivity and mechanical properties.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of lithium germanium phosphorus sulfur used for an all-solid-state battery material specifically comprises the following steps:
(1) mixing a lithium compound, a germanium compound and a phosphorus compound, tabletting, carrying out heat treatment, cooling and then carrying out ball milling to obtain a sulfur-based solid electrolyte;
wherein the lithium compound is a mixture of lithium sulfide and lithium oxide, the germanium compound is a mixture of germanium sulfide and germanium oxide, and the phosphorus compound is a mixture of phosphorus pentasulfide and phosphorus pentaoxide;
(2) uniformly mixing resin and lithium salt to obtain an organic solid electrolyte;
(3) uniformly mixing the sulfur-based solid electrolyte and the organic solid electrolyte to obtain a base material;
(4) adding the base material into the impregnation liquid for impregnation, and then drying and curing under a vacuum condition to obtain the lithium germanium phosphorus sulfur used for the all-solid-state battery material;
wherein the impregnation liquid is at least one of dimethyl sulfoxide, dimethyl sulfite and N, N-dimethylformamide; the temperature for drying and curing is 120-160 ℃, and the time is 2-4 h.
Further, in the step (1), the molar ratio of the lithium compound, the germanium compound and the phosphorus compound is (3-5) to (1-2) to (2-4); the pressure of the tabletting is 200-300 MPa; the temperature of the heat treatment is 650-750 ℃, and the time is 3-4 h; the ball milling speed is 350-500r/min, and the time is 15-72 h.
The invention has the advantages that the invention takes the lithium compound, the germanium compound and the phosphorus compound as raw materials, and can obtain the crystalline sulfur-based solid electrolyte by mixing, tabletting, heat treatment and ball milling, thereby providing a multidimensional channel for lithium ion transmission, increasing the disorder degree of lithium ion distribution, and further improving the lithium ion conductivity and the electrochemical stability of the sulfur-based solid electrolyte.
Further, in the step (2), the resin is at least one of polyethylene oxide, polyacrylonitrile and polyethylene glycol polyacrylate; the lithium salt is at least one of lithium perchlorate, lithium dioxalate borate and lithium bistrifluoromethanesulfonylimide; the mass ratio of the resin to the lithium salt is (3-10) to (1-2).
The resin material selected by the invention has the advantages of light weight, good viscoelasticity, easy film formation, good electrochemical and chemical stability and high transference number of lithium ions; the organic solid electrolyte prepared by mixing the resin and the lithium salt forms a transmission channel of lithium ions in an organic matter part.
Further, in the step (3) above, the mass ratio of the sulfur-based solid electrolyte to the organic solid electrolyte is (4-6): (5-8).
Further, in the step (4), the soaking time is 12-24 h; the degree of vacuum under vacuum was (-0.06) - (-0.1) MPa.
The beneficial effect of adopting the further technical scheme is that the sulfur-based solid electrolyte and the organic solid electrolyte are mixed and then are soaked, dried and solidified, so that the sulfur-based solid electrolyte can be coated by the organic solid electrolyte in situ, and the interface resistance among the sulfur-based solid electrolyte particles is effectively reduced because the organic solid electrolyte can be filled among the inorganic electrolyte particles, so that the ionic conductivity of the solid electrolyte at room temperature is further improved.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the organic solid electrolyte coats the surface of the sulfur-based solid electrolyte, so that direct contact between the metal lithium and the sulfur-based solid electrolyte is isolated, and the interface reaction between the sulfur-based solid electrolyte and the metal lithium cathode is inhibited, so that the solid electrolyte and the metal lithium have good interface compatibility.
2. The dry curing under vacuum conditions can prevent the solid electrolyte from being deteriorated by exposure to moisture and air.
3. The sulfur-based solid electrolyte and the organic solid electrolyte are combined to prepare the composite solid electrolyte, so that the advantages of the sulfur-based solid electrolyte and the organic solid electrolyte can be effectively combined to form the solid electrolyte with good lithium ion conductivity, electrochemical stability and mechanical property.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the lithium germanium phosphorus sulfur used for the all-solid-state battery material specifically comprises the following steps:
(1) mixing a mixture of lithium sulfide and lithium oxide, a mixture of germanium sulfide and germanium oxide, and a mixture of phosphorus pentasulfide and phosphorus pentaoxide in a molar ratio of 3:2:4, pressing into tablets under the action of a tablet press at 200MPa, heating to 650 ℃, carrying out heat treatment for 4 hours, cooling, and carrying out ball milling for 72 hours at a speed of 350r/min to obtain a sulfur-based solid electrolyte;
(2) uniformly mixing polyoxyethylene and lithium perchlorate in a mass ratio of 3:2 to obtain an organic solid electrolyte;
(3) uniformly mixing the sulfur-based solid electrolyte and the organic solid electrolyte in a mass ratio of 4:8 to obtain a base material;
(4) adding the base material into dimethyl sulfoxide for soaking for 12h, and then heating to 120 ℃ under the vacuum condition of the vacuum degree of-0.06 MPa for drying and curing for 4h to obtain the lithium-germanium-phosphorus-sulfur material for the all-solid-state battery.
Example 2
The preparation method of the lithium germanium phosphorus sulfur used for the all-solid-state battery material specifically comprises the following steps:
(1) mixing a mixture of lithium sulfide and lithium oxide, a mixture of germanium sulfide and germanium oxide, and a mixture of phosphorus pentasulfide and phosphorus pentaoxide in a molar ratio of 4:1:3, pressing into tablets under the action of 250MPa of a tablet press, heating to 700 ℃ for heat treatment for 4h, cooling, and performing ball milling for 48h at a speed of 400r/min to obtain a sulfur-based solid electrolyte;
(2) uniformly mixing polyacrylonitrile and lithium dioxalate borate in a mass ratio of 5:2 to obtain an organic solid electrolyte;
(3) uniformly mixing the sulfur-based solid electrolyte and the organic solid electrolyte in a mass ratio of 5:7 to obtain a base material;
(4) adding the base material into dimethyl sulfite for soaking for 18h, and then heating to 140 ℃ under the vacuum condition of the vacuum degree of-0.08 MPa for drying and curing for 3h to obtain the lithium germanium phosphorus sulfur used for the all-solid-state battery material.
Example 3
The preparation method of the lithium germanium phosphorus sulfur used for the all-solid-state battery material specifically comprises the following steps:
(1) mixing a mixture of lithium sulfide and lithium oxide, a mixture of germanium sulfide and germanium oxide, and a mixture of phosphorus pentasulfide and phosphorus pentaoxide in a molar ratio of 5:1:2, pressing into tablets under the action of 300MPa of a tablet press, heating to 750 ℃, carrying out heat treatment for 3h, cooling, and carrying out ball milling for 15h at a speed of 500r/min to obtain a sulfur-based solid electrolyte;
(2) uniformly mixing polyethylene glycol acrylate and lithium bis (trifluoromethanesulfonyl) imide in a mass ratio of 10:1 to obtain an organic solid electrolyte;
(3) uniformly mixing the sulfur-based solid electrolyte and the organic solid electrolyte in a mass ratio of 6:5 to obtain a base material;
(4) adding the base material into N, N-dimethylformamide for soaking for 24h, then heating to 160 ℃ under the vacuum condition that the vacuum degree is-0.1 MPa, drying and curing for 2h, and obtaining the lithium-germanium-phosphorus-sulfur material for the all-solid battery.
Comparative example 1
The only difference from example 2 is that no organic solid electrolyte was added.
Comparative example 2
Only the difference from example 2 is that no sulfur-based solid electrolyte was added.
Performance testing
1. Lithium ion conductivity test
The lithium ion conductivities of the solid electrolytes prepared in examples 1 to 3 and comparative examples 1 to 2 were measured, respectively. The results are shown in Table 1.
Table 1 examples 1 to 3 and comparative examples 1 to 2 solid electrolyte lithium ion conductivity test results
| Test sample | Lithium ion conductivity (S/cm) |
| Example 1 | 1.14×10-3 |
| Example 2 | 1.32×10-3 |
| Example 3 | 1.28×10-3 |
| Comparative example 1 | 2.15×10-5 |
| Comparative example 2 | 2.75×10-5 |
As can be seen from table 1, the lithium ion conductivity of the solid electrolytes prepared in examples 1 to 3 of the present invention was significantly improved as compared to comparative example 1 in which no organic solid electrolyte was added and comparative example 2 in which no sulfur-based solid electrolyte was added. Among them, the embodiment 2 is the most preferable embodiment.
The above experiments show that the lithium germanium phosphorus sulfur used as the all-solid-state battery material has good lithium ion conductivity.
2. Electrochemical stability and mechanical Property testing
All-solid batteries were prepared separately from the solid electrolyte prepared in example 2. The preparation method comprises the following steps: dissolving 0.06g of nickel-cobalt-manganese ternary positive electrode active material, 0.01g of Super P, 0.03g of polyoxyethylene (10,0000) and 0.01g of lithium bis (trifluoromethanesulfonyl) imide in 5mL of dimethyl amide, and stirring at 60 ℃ for 5 hours to obtain a uniform positive electrode precursor solution; then casting the mixture on a solid electrolyte, and drying the mixture in vacuum at 80 ℃ for 12 hours to obtain a positive electrode and the solid electrolyte which are in close contact; and transferring the lithium ion battery to an argon glove box, and assembling the lithium ion battery into an all-solid-state battery by taking a metal lithium sheet as a negative electrode.
Setting the charging and discharging voltage range to be 1.4-3.6V, the charging and discharging multiplying power to be 0.1C, and the testing temperature to be room temperature, carrying out charging and discharging tests in a flat and bent state, and recording the cycle times and the specific discharging capacity. The results are shown in tables 2 and 3.
Table 2 example 2 test results of the leveling state of all-solid-state battery
| Number of cycles | Specific discharge capacity (mAh/g) |
| 1 | 182.5 |
| 5 | 184.2 |
| 10 | 185.7 |
| 15 | 179.6 |
| 20 | 178.5 |
As can be seen from Table 2, in the flat state, the initial cycle specific discharge capacity of the all-solid-state battery can reach 182.5mAh/g, the 10-cycle capacity retention rate can reach 100%, and the 20-cycle capacity retention rate is 97.81%.
Table 3 example 2 all-solid-state battery bending state test results
| Number of cycles | Specific discharge capacity (mAh/g) |
| 1 | 185.6 |
| 5 | 183.9 |
| 10 | 184.7 |
| 15 | 180.2 |
| 20 | 179.1 |
As can be seen from Table 3, in the bent state, the discharge specific capacity of the all-solid-state battery in the initial cycle can reach 185.6mAh/g, the cycle capacity retention rate for 10 times is 99.52%, and the cycle capacity retention rate for 20 times is still 96.50%. This is not significantly different from the discharge performance of the all-solid battery in the flat state.
The tests show that the lithium, germanium, phosphorus and sulfur used as the all-solid-state battery material has good electrochemical stability and mechanical property.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of lithium germanium phosphorus sulfur used for an all-solid-state battery material is characterized by comprising the following steps:
(1) mixing a lithium compound, a germanium compound and a phosphorus compound, tabletting, carrying out heat treatment, cooling and then carrying out ball milling to obtain a sulfur-based solid electrolyte;
wherein the lithium compound is a mixture of lithium sulfide and lithium oxide, the germanium compound is a mixture of germanium sulfide and germanium oxide, and the phosphorus compound is a mixture of phosphorus pentasulfide and phosphorus pentaoxide;
(2) uniformly mixing resin and lithium salt to obtain an organic solid electrolyte;
(3) uniformly mixing the sulfur-based solid electrolyte and the organic solid electrolyte to obtain a base material;
(4) adding the base material into the impregnation liquid for impregnation, and then drying and curing under a vacuum condition to obtain the lithium germanium phosphorus sulfur used for the all-solid-state battery material;
wherein the impregnation liquid is at least one of dimethyl sulfoxide, dimethyl sulfite and N, N-dimethylformamide;
the temperature for drying and curing is 120-160 ℃, and the time is 2-4 h.
2. The method for preparing lithium germanium phosphorus sulfur as claimed in claim 1, wherein the molar ratio of the lithium compound, the germanium compound and the phosphorus compound in step (1) is (3-5): (1-2): (2-4).
3. The method as claimed in claim 1, wherein the pressure of the pellet in step (1) is 200-300 MPa.
4. The method as claimed in claim 1, wherein the heat treatment temperature in step (1) is 650-750 ℃ for 3-4 h.
5. The method as claimed in claim 1, wherein in step (1), the ball milling speed is 350-500r/min, and the time is 15-72 h.
6. The method for preparing lithium germanium phosphorus sulfide for all-solid-state battery material according to claim 1, wherein in the step (2), the resin is at least one of polyethylene oxide, polyacrylonitrile and polyethylene glycol polyacrylate.
7. The method for preparing lithium germanium phosphorus sulfide for all-solid-state battery material according to claim 1, wherein in the step (2), the lithium salt is at least one of lithium perchlorate, lithium dioxalate borate and lithium bistrifluoromethanesulfonylimide.
8. The method for preparing lithium germanium phosphorus sulfur as claimed in claim 1, wherein in the step (2), the mass ratio of the resin to the lithium salt is (3-10) to (1-2).
9. The method for preparing lithium germanium phosphorus sulfur as claimed in claim 1, wherein the mass ratio of the sulfur-based solid electrolyte to the organic solid electrolyte in step (3) is (4-6) to (5-8).
10. The method for preparing lithium germanium phosphorus sulfur as an all-solid battery material according to claim 1, wherein in the step (3), the immersion time is 12-24 h; the vacuum degree under the vacuum condition is (-0.06) - (-0.1) MPa.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888373A (en) * | 2018-12-27 | 2019-06-14 | 山东大学 | A kind of organic/inorganic composite solid electrolyte and preparation method thereof |
| CN110085904A (en) * | 2019-05-08 | 2019-08-02 | 中国空间技术研究院 | Flexible compound solid electrolyte, all-solid lithium-ion battery and preparation method thereof |
| US20200112050A1 (en) * | 2017-03-29 | 2020-04-09 | University Of Maryland, College Park | Solid-state hybrid electrolytes, methods of making same, and uses thereof |
| CN111244409A (en) * | 2020-01-15 | 2020-06-05 | 东南大学 | Solid electrolyte-anode composite material and preparation and application thereof |
| JP2020198270A (en) * | 2019-06-05 | 2020-12-10 | 日産自動車株式会社 | Solid-state electrolyte layer for all-solid-state lithium-ion secondary battery and all-solid-state lithium-ion secondary battery including the same |
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- 2021-09-24 CN CN202111126248.9A patent/CN113851700A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200112050A1 (en) * | 2017-03-29 | 2020-04-09 | University Of Maryland, College Park | Solid-state hybrid electrolytes, methods of making same, and uses thereof |
| CN109888373A (en) * | 2018-12-27 | 2019-06-14 | 山东大学 | A kind of organic/inorganic composite solid electrolyte and preparation method thereof |
| CN110085904A (en) * | 2019-05-08 | 2019-08-02 | 中国空间技术研究院 | Flexible compound solid electrolyte, all-solid lithium-ion battery and preparation method thereof |
| JP2020198270A (en) * | 2019-06-05 | 2020-12-10 | 日産自動車株式会社 | Solid-state electrolyte layer for all-solid-state lithium-ion secondary battery and all-solid-state lithium-ion secondary battery including the same |
| CN111244409A (en) * | 2020-01-15 | 2020-06-05 | 东南大学 | Solid electrolyte-anode composite material and preparation and application thereof |
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