CN112072167A - Method for compounding metal lithium and carbon nano tube for inorganic solid-state lithium metal battery - Google Patents
Method for compounding metal lithium and carbon nano tube for inorganic solid-state lithium metal battery Download PDFInfo
- Publication number
- CN112072167A CN112072167A CN202010947541.0A CN202010947541A CN112072167A CN 112072167 A CN112072167 A CN 112072167A CN 202010947541 A CN202010947541 A CN 202010947541A CN 112072167 A CN112072167 A CN 112072167A
- Authority
- CN
- China
- Prior art keywords
- lithium
- lithium metal
- solid
- metal
- solid electrolyte
- 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
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
-
- 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)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of lithium batteries, and particularly discloses a method for compounding metal lithium and carbon nanotubes for an inorganic solid-state lithium metal battery, which comprises the following steps: s1, polishing and grinding the solid electrolyte substrate; s2, melting lithium in a glove box filled with Ar gas; s3, adding a proper amount of carbon nano tubes into the molten metal lithium, and uniformly mixing; s4, soaking the molten mixture on the surface of the solid electrolyte; s5, scraping the mixture by using tweezers to promote the molten mixture to be uniformly coated on the surface of the solid electrolyte; s6, obtaining a solid lithium metal anode with well-infiltrated mixed nano-tubes; and S7, assembling the whole battery. The method can effectively regulate and control the deposition of the lithium metal, improve the capacity of the solid-state battery and effectively inhibit the formation of lithium metal dendrites.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a method for compounding metal lithium and carbon nano tubes to an inorganic solid-state lithium metal battery.
Background
In the face of the continuous environmental and energy crisis problems of the present society, the research and development of batteries with high specific power, high specific energy, high endurance mileage and high safety are urgent, but the current development and application of commercial lithium ion batteries almost reach the limit value of the theoretical specific capacity, but the requirements of the existing energy storage equipment on the battery performance cannot be met. To improve the energy density of the battery, it is desirable to use lithium metal as the anode because when lithium metal is used as the battery electrode, it exhibits the most negative potential (-3.04Vvs standard hydrogen electrode), and the capacity of the lithium metal negative electrode exhibits a theoretical specific capacity of 3860mAh g-1, calculated based on the lithium metal itself. Lithium metal is selected as an anode material, and the problem of matching with an electrolyte is needed to be considered, however, most of the existing commercial lithium ion batteries adopt a liquid electrolyte, and one of the most troublesome problems of the liquid electrolyte is that the liquid electrolyte mostly contains a flammable organic solvent, so that a series of side reactions occur between the lithium metal and the liquid organic electrolyte, the battery finally fails, and more seriously, safety problems such as fire, explosion and the like occur. Therefore, researchers turn their attention to a solid electrolyte which is relatively more stable when matched with lithium metal, and assume that a solid lithium metal battery which has both high specific capacity and high safety is constructed.
However, for the realization of commercial application of solid-state lithium metal batteries, the key, focus and neck problems of lithium metal negative electrodes are. Since the metallic lithium negative electrode is a conversion type negative electrode. Different from other conversion type cathodes (such as silicon, carbon, tin and the like), the metal lithium is a conversion type cathode with conductivity because the metal lithium has an electronic channel, and in the process of charging and discharging of a solid-state battery, dendritic crystal growth can be caused due to uneven deposition of the metal lithium, so that irreversible capacity loss of the metal lithium is caused, finally capacity of the battery is reduced, failure is caused, even a series of safety problems are caused, the battery utilization rate and the service life in the actual operation process of the battery are seriously influenced, and the commercialization process of the solid-state metal lithium battery is limited. Therefore, it is urgent to find an effective method to regulate the uniform deposition of a metallic lithium negative electrode in order to realize the commercialization process of a solid-state lithium metal battery early.
Disclosure of Invention
The invention aims to provide a method for compounding metal lithium and carbon nanotubes for an inorganic solid lithium metal battery, which can effectively regulate and control the deposition of the metal lithium, improve the capacity of the solid battery and effectively inhibit the formation of lithium metal dendrites.
In order to solve the technical problem, the invention provides a method for compounding metal lithium and carbon nanotubes for an inorganic solid-state lithium metal battery, which comprises the following steps:
s1, polishing and grinding the solid electrolyte substrate;
s2, melting lithium in a glove box filled with Ar gas;
s3, adding a proper amount of carbon nano tubes into the molten metal lithium, and uniformly mixing;
s4, soaking the molten mixture on the surface of the solid electrolyte;
s5, scraping the mixture by using tweezers to promote the molten mixture to be uniformly coated on the surface of the solid electrolyte;
s6, obtaining a solid lithium metal anode with well-infiltrated mixed nano-tubes;
and S7, assembling the whole battery.
Preferably, the mass fraction of the carbon nanotube is 0.1-30%.
Preferably, the carbon nanotubes are replaced by graphene.
Preferably, the solid electrolyte is a garnet-type inorganic solid electrolyte.
Preferably, the temperature inside the glove box is greater than 180 ℃.
The invention has the following beneficial effects:
1. the cost is low. The heating device, glove box and other equipment required by the process are mature on the market and easy to purchase, and compared with the magnetron sputtering technology, the magnetron sputtering technology does not need to have high requirements on a reaction device and a reflection environment and has low process cost.
2. The process is simple. The method is characterized in that the method only needs to mix and soak the nanotubes and lithium uniformly in a molten state and then directly apply the mixture on the surface of a solid electrolyte, only needs inert atmosphere protection in the process, does not need other processes, and has multi-aspect condition control, for example, electrodeposition needs to strictly control the flatness of copper foil, otherwise dendritic crystal growth is aggravated.
3. Is safe and reliable. Rolling and winding are not needed like a mechanical method, and harsh environmental temperature is not needed.
Drawings
Fig. 1 is a flow chart of a method provided by an embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
Referring to fig. 1, the method comprises the following steps:
i: polishing and grinding the surface of the solid electrolyte (garnet inorganic solid electrolyte is selected) to be infiltrated in the experiment, and removing a series of impurities such as lithium carbonate, lithium hydroxide and the like generated on the surface when a high-temperature sintering person contacts the air, thereby creating good conditions for the next infiltration;
II: because the lithium metal is easy to react with water and oxygen in the air, the reaction needs to be operated in an Ar gas atmosphere filled with rare gas;
III: adding the weighed nanotubes (with the mass fraction of 0.1-30%) into molten metal, and using tweezers to assist in fully reacting and uniformly mixing;
IV: transferring the molten mixture to the surface of a solid electrolyte;
v: using tweezers as an assistant to guide the mixture to be uniformly soaked on the surface of the solid electrolyte; +
VI: the solid lithium metal battery with well-infiltrated anode uniformly mixed with the carbon nano tube as a framework is obtained;
VII: a full cell assembly is performed and then the next step of relevant performance testing studies can be performed.
In particular, the method of the preferred embodiment of the present invention is less costly. The heating device, glove box and other equipment required by the process are mature on the market and easy to purchase, and compared with the magnetron sputtering technology, the magnetron sputtering technology does not need to have high requirements on a reaction device and a reflection environment and has low process cost. The process is simple; the method is characterized in that the method only needs to mix and soak the nanotubes and lithium uniformly in a molten state and then directly apply the mixture on the surface of a solid electrolyte, only needs inert atmosphere protection in the process, does not need other processes, and has multi-aspect condition control, for example, electrodeposition needs to strictly control the flatness of copper foil, otherwise dendritic crystal growth is aggravated. The safety and the reliability are realized; rolling and winding are not needed like a mechanical method, and harsh environmental temperature is not needed.
In a preferred embodiment of the invention, the mass fraction of the carbon nanotubes is 0.1-30%.
In a preferred embodiment of the present invention, the carbon nanotubes are replaced with graphene.
In a preferred embodiment of the present invention, the solid electrolyte is a garnet-type inorganic solid electrolyte.
In a preferred embodiment of the invention, the temperature inside the glove box is greater than 180 ℃.
Specifically, compared with the prior art, the method has the advantages that the carbon nano tubes are mixed in the molten lithium metal in a certain proportion and are uniformly soaked on the solid electrolyte, and compared with the prior art, the method has the advantages that the carbon nano tubes are uniformly mixed in the molten lithium metal at a high temperature, so that when the carbon nano tubes are used as the lithium metal anode, a framework constructed by the carbon nano tubes can play a role in effectively regulating and controlling uniform deposition of the lithium metal, the capacity of the solid lithium metal battery can be further improved to a certain extent, the safety performance of the solid battery is greatly improved, and the high-safety and high-capacity solid lithium metal battery is realized.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and substitutions can be made without departing from the technical principle of the present invention, and these modifications and substitutions should also be regarded as the protection scope of the present invention.
Claims (5)
1. A method for compounding metallic lithium and carbon nanotubes for an inorganic solid-state lithium metal battery is characterized by comprising the following steps:
s1, polishing and grinding the solid electrolyte substrate;
s2, melting lithium in a glove box filled with Ar gas;
s3, adding a proper amount of carbon nano tubes into the molten metal lithium, and uniformly mixing;
s4, soaking the molten mixture on the surface of the solid electrolyte;
s5, scraping the mixture by using tweezers to promote the molten mixture to be uniformly coated on the surface of the solid electrolyte;
s6, obtaining a solid lithium metal anode with well-infiltrated mixed nano-tubes;
and S7, assembling the whole battery.
2. The method for compounding metallic lithium and carbon nanotubes for an inorganic solid-state lithium metal battery according to claim 1, wherein: the mass fraction of the carbon nano tube is 0.1-30%.
3. The method for compounding metallic lithium and carbon nanotubes for an inorganic solid state lithium metal battery according to claim 1, wherein the carbon nanotubes are replaced with graphene.
4. The method for compounding metallic lithium and carbon nanotubes for use in an inorganic solid-state lithium metal battery according to claim 1, wherein the solid electrolyte is a garnet-type inorganic solid electrolyte.
5. The method for compounding lithium metal and carbon nanotubes for use in an inorganic solid state lithium metal battery as claimed in claim 1, wherein the temperature inside the glove box is greater than 180 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010947541.0A CN112072167A (en) | 2020-09-10 | 2020-09-10 | Method for compounding metal lithium and carbon nano tube for inorganic solid-state lithium metal battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010947541.0A CN112072167A (en) | 2020-09-10 | 2020-09-10 | Method for compounding metal lithium and carbon nano tube for inorganic solid-state lithium metal battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112072167A true CN112072167A (en) | 2020-12-11 |
Family
ID=73663434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010947541.0A Pending CN112072167A (en) | 2020-09-10 | 2020-09-10 | Method for compounding metal lithium and carbon nano tube for inorganic solid-state lithium metal battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112072167A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114171799A (en) * | 2021-11-19 | 2022-03-11 | 哈尔滨工业大学 | Method for improving wettability of lithium on surface of solid electrolyte and all-solid-state battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN204608129U (en) * | 2014-12-29 | 2015-09-02 | 天津中能锂业有限公司 | A kind of metallic lithium melt production device |
| US20170133662A1 (en) * | 2015-11-11 | 2017-05-11 | The Board Of Trustees Of The Leland Stanford Junior University | Composite lithium metal anodes for lithium batteries with reduced volumetric fluctuation during cycling and dendrite suppression |
| CN109841811A (en) * | 2019-01-09 | 2019-06-04 | 同济大学 | A kind of lithium base negative electrode material and the preparation method and application thereof for solid state battery |
| CN110660968A (en) * | 2019-09-17 | 2020-01-07 | 天津大学 | Composite lithium metal negative electrode and preparation method thereof |
| CN111162265A (en) * | 2020-01-17 | 2020-05-15 | 中国人民解放军国防科技大学 | Preparation method of metal lithium composite negative electrode for solid-state battery |
| CN111224066A (en) * | 2020-02-11 | 2020-06-02 | 五邑大学 | Method for regulating interface between solid electrolyte and metal lithium cathode |
-
2020
- 2020-09-10 CN CN202010947541.0A patent/CN112072167A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN204608129U (en) * | 2014-12-29 | 2015-09-02 | 天津中能锂业有限公司 | A kind of metallic lithium melt production device |
| US20170133662A1 (en) * | 2015-11-11 | 2017-05-11 | The Board Of Trustees Of The Leland Stanford Junior University | Composite lithium metal anodes for lithium batteries with reduced volumetric fluctuation during cycling and dendrite suppression |
| CN109841811A (en) * | 2019-01-09 | 2019-06-04 | 同济大学 | A kind of lithium base negative electrode material and the preparation method and application thereof for solid state battery |
| CN110660968A (en) * | 2019-09-17 | 2020-01-07 | 天津大学 | Composite lithium metal negative electrode and preparation method thereof |
| CN111162265A (en) * | 2020-01-17 | 2020-05-15 | 中国人民解放军国防科技大学 | Preparation method of metal lithium composite negative electrode for solid-state battery |
| CN111224066A (en) * | 2020-02-11 | 2020-06-02 | 五邑大学 | Method for regulating interface between solid electrolyte and metal lithium cathode |
Non-Patent Citations (1)
| Title |
|---|
| JIAN DUAN ET AL.: "Lithium–Graphite Paste: An Interface Compatible Anode for Solid-State Batteries", 《ADVANCED MATERIALS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114171799A (en) * | 2021-11-19 | 2022-03-11 | 哈尔滨工业大学 | Method for improving wettability of lithium on surface of solid electrolyte and all-solid-state battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111785974B (en) | Positive electrode coating method for sulfide solid-state lithium ion battery, positive electrode and battery | |
| Bruce et al. | Lithium-air and lithium-sulfur batteries | |
| Guo et al. | Progress in electrode materials for the industrialization of sodium-ion batteries | |
| EP4290609A1 (en) | Negative electrode material, composite negative electrode material and preparation method therefor, secondary battery, and terminal device | |
| Wang et al. | How to promote the industrial application of SiOx anode prelithiation: capability, accuracy, stability, uniformity, cost, and safety | |
| Li et al. | Prelithiation bridges the gap for developing next‐generation lithium‐ion batteries/capacitors | |
| Zhou et al. | High performance Si/MgO/graphite composite as the anode for lithium-ion batteries | |
| CN102412402B (en) | Method for preparing discontinuous graphene coated lithium ion battery electrode material | |
| CN114649562B (en) | Preparation and application of IIA group element and dihalogen doped sulfide solid electrolyte | |
| Song et al. | A Review on the Features and Progress of Silicon Anodes‐Based Solid‐State Batteries | |
| CN112563448A (en) | Method for treating SEI (solid electrolyte interphase) film on interface of low-temperature-resistant lithium ion battery | |
| CN111320161A (en) | Preparation method and application of asphalt-based carbon nanosheet | |
| CN117154012A (en) | Sulfide all-solid-state battery and preparation method thereof | |
| CN111916721A (en) | Magnesium-sulfur secondary battery with magnesium-lithium alloy as negative electrode | |
| CN112072167A (en) | Method for compounding metal lithium and carbon nano tube for inorganic solid-state lithium metal battery | |
| CN112768756B (en) | Solid electrolyte material, and composite solid electrolyte and all-solid-state battery prepared from same | |
| CN111952598B (en) | Negative plate, preparation method thereof and secondary battery | |
| CN114005982A (en) | In-situ functional coated cathode material, preparation method thereof and all-solid-state lithium battery | |
| CN113871605A (en) | Pre-lithiated silicon-based negative electrode material and preparation method and application thereof | |
| CN115411351A (en) | Solid-state battery modified by ion/electron mixed conductive solid interface layer and preparation method thereof | |
| CN103730636B (en) | Prepare high potential LiNi 0.5mn 1.5o 4based lithium-ion battery positive plate method | |
| CN116960444A (en) | Preparation method of high-voltage stable lithium borohydride-based solid electrolyte, product and application thereof | |
| CN111682210B (en) | Positive electrode material, preparation method thereof and secondary battery | |
| Yasin et al. | Lithium metal anode: an introduction | |
| Li et al. | Pre‐Lithiation Technology for Rechargeable Lithium‐Ion Batteries: Principles, Applications, and Perspectives |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201211 |