CN114566613A - High-stability composite lithium negative electrode - Google Patents
High-stability composite lithium negative electrode Download PDFInfo
- Publication number
- CN114566613A CN114566613A CN202210206689.8A CN202210206689A CN114566613A CN 114566613 A CN114566613 A CN 114566613A CN 202210206689 A CN202210206689 A CN 202210206689A CN 114566613 A CN114566613 A CN 114566613A
- Authority
- CN
- China
- Prior art keywords
- lithium
- negative electrode
- copper foil
- composite lithium
- array structure
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011889 copper foil Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 abstract description 9
- 238000007599 discharging Methods 0.000 abstract description 8
- 210000001787 dendrite Anatomy 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 230000006911 nucleation Effects 0.000 abstract 1
- 238000010899 nucleation Methods 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Abstract
A high-stability composite lithium cathode relates to the field of lithium ion batteries. The structure of the graphene/lithium-ion battery comprises a copper foil substrate with good conductive performance, a vertically grown graphene interconnection array structure with a micropore structure and metal lithium filled in the micropore. The graphene interconnection array structure with the vertical growth of the microporous structure grows on the surface of the copper foil, has a huge specific surface area, is physically connected with the surface of the copper foil, and can greatly reduce the interface impedance of the composite lithium cathode. The structure can reduce the nucleation overpotential of lithium atoms, and can reduce the local current density of the battery in the charging and discharging process, thereby inhibiting the growth of lithium dendrites and improving the electrochemical stability of the composite lithium cathode. In addition, the composite lithium negative electrode with the porous structure provides enough space for metal lithium, and eliminates the volume change effect of the composite lithium negative electrode in the charging and discharging processes.
Description
Technical Field
The invention relates to a high-stability composite lithium cathode, and belongs to the field of lithium ion batteries.
Technical Field
With the rapid development of electronic devices and electric automobiles, the most advanced lithium ion batteries commercialized at present still have an energy density bottleneck (-200 Wh/kg), and thus are difficult to meet our practical requirements. One potential solution is to replace the commercial graphite anodes currently in use with lithium metal anodes, using their high theoretical capacity (3860mA h/g) and low operating voltage (-3.04V ratio standard hydrogen electrodes) to meet our actual needs. However, despite the excellent application potential of lithium cathodes, there are still some serious problems hindering practical applications: first, the intrinsic reactivity of lithium metal with the electrolyte at low potentials results in its rapid depletion and promotes the formation of irreversible solid-electrolyte interphase (SEI). Second, the mechanical instability of the SEI can result in dendritic lithium at the Li-SEI surface, an excessively thick SEI layer, or disconnected "dead lithium" due to large electrode volume changes caused by repeated lithium deposition and exfoliation, all of which ultimately create a safety hazard and low coulombic efficiency. Therefore, comprehensive research into the suppression of lithium dendrites is crucial to the practical application of lithium metal batteries.
Disclosure of Invention
The invention aims to avoid the defects in the prior art and provide the high-stability composite lithium negative electrode, which can reduce the deposition overpotential of lithium atoms, reduce the local current density in the charging and discharging process, induce the uniform deposition of the lithium atoms, inhibit the growth of lithium dendrites, provide a stable deposition space for metal lithium on the negative electrode, eliminate the volume change of a battery in the charging and discharging process and greatly improve the cycle stability of the battery.
The purpose of the invention is realized by the following technical scheme:
a high-stability composite lithium negative electrode comprises a copper foil substrate with a proper thickness, a vertically grown graphene interconnection array structure with a micropore structure and metal lithium filled in the micropore, wherein the graphene interconnection array structure is in physical connection with the copper foil substrate.
In the technical scheme, the copper foil substrate is 6-30 microns thick and has good conductivity.
In the technical scheme, the graphene interconnection array structure with the vertical growth of the microporous structure is grown on the surface of the copper foil substrate by using a PECVD method, and is physically connected with the copper foil substrate, and the interface belongs to ohmic contact.
In the above technical solution, the thickness of the graphene interconnection array structure is 10-100 micrometers.
In the technical scheme, micropores of the graphene interconnection array structure are filled with metal lithium, and the filling amount is 10% -90%.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
the high-stability composite lithium negative electrode can reduce the deposition overpotential of lithium atoms, reduce the local current density in the charging and discharging process, induce the uniform deposition of the lithium atoms and inhibit the growth of lithium dendrites.
The high-stability composite lithium negative electrode provides a stable deposition space for the metal lithium in the negative electrode, and eliminates the volume change of the battery in the charging and discharging processes.
And thirdly, the high-stability composite lithium negative electrode greatly improves the cycling stability of the composite lithium negative electrode.
And fourthly, the high-stability composite lithium cathode is simple to manufacture, low in cost and suitable for large-scale production of lithium ion battery cathodes.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and other drawings can be derived by those skilled in the art without inventive effort from the following drawings.
Fig. 1 shows a high stability composite lithium negative electrode of the present invention.
Fig. 2 shows the cycling stability of a high stability composite lithium negative electrode symmetric battery of the present invention.
Fig. 3 shows the cycle stability of a high stability composite lithium negative electrode full cell according to the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
In order to facilitate an understanding of the invention, the invention will be further explained below with reference to the accompanying drawings. The accompanying drawings illustrate an exemplary embodiment of the present invention. The invention may, however, be embodied in many different forms and is not limited to the embodiments. Rather, this embodiment is shown for the purpose of illustrating the disclosure of the present invention in more detail.
As shown in fig. 1, this example shows a structure of a high-stability composite lithium negative electrode. The graphene/lithium-ion battery comprises a substrate made of copper foil, a vertically grown graphene interconnection array structure with a micropore structure and metal lithium filled in the micropores.
The thickness of the copper foil was 30 μm.
The thickness of the microporous structure vertically grown graphene interconnection array structure is 20 micrometers.
The metal lithium filling amount of the graphene interconnection array structure with the vertically grown microporous structure is 80%.
FIG. 2 shows a symmetrical long cycle plot of a high stability composite lithium negative electrode as an electrode for a cell with a current density of 1mA cm-2The total capacity is 1mA h cm-2Can stably circulate for 1000h under the condition, and the composite electrode greatly improves the circulation stability of the symmetrical battery. .
As shown in fig. 3, this example shows a full-cell long cycle diagram of a high-stability composite lithium negative electrode as a negative electrode, which can be stably cycled for 400 cycles at 1C, with a capacity retention rate of 90%, and thus shows excellent cycle stability in a full cell.
The high-stability composite lithium negative electrode shown in the embodiment effectively reduces the deposition overpotential of lithium atoms under the synergistic effect of the high-conductivity copper foil substrate and the graphene interconnection array structure vertically grown by the large-specific-surface microporous structure, reduces the local current density in the charging and discharging process, induces the uniform deposition of the lithium atoms, inhibits the growth of lithium dendrites, provides a stable deposition space for metal lithium at the negative electrode, eliminates the volume change of a battery in the charging and discharging process, and greatly improves the cycling stability of the metal lithium as the negative electrode of the lithium ion battery.
Claims (6)
1. A high-stability composite lithium negative electrode is characterized in that: the graphene/lithium-ion battery comprises a copper foil substrate with a proper thickness, a vertically grown graphene interconnection array structure with a micropore structure and metal lithium filled in the micropore, wherein the graphene interconnection array structure is in physical connection with the copper foil substrate.
2. The high-stability composite lithium negative electrode as claimed in claim 1, wherein the copper foil substrate has a thickness of 6-30 μm and good conductivity.
3. The high-stability composite lithium negative electrode as claimed in claim 1, wherein a layer of vertically grown graphene interconnection array structure with a microporous structure is grown on the surface of the copper foil substrate.
4. The vertically grown graphene interconnection array structure with a microporous structure of claim 2, wherein the graphene interconnection array structure is physically connected with a copper foil substrate, and the interface is ohmic contact.
5. The layer of vertically grown graphene interconnection array structure with microporous structure of claim 2, wherein the thickness of the graphene interconnection array structure is 10-100 μm.
6. The high-stability composite lithium negative electrode as claimed in claim 1, wherein micropores of the graphene interconnection array structure are filled with lithium metal, and the filling amount is 10% -90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210206689.8A CN114566613A (en) | 2022-03-03 | 2022-03-03 | High-stability composite lithium negative electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210206689.8A CN114566613A (en) | 2022-03-03 | 2022-03-03 | High-stability composite lithium negative electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114566613A true CN114566613A (en) | 2022-05-31 |
Family
ID=81718373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210206689.8A Pending CN114566613A (en) | 2022-03-03 | 2022-03-03 | High-stability composite lithium negative electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114566613A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108063218A (en) * | 2017-12-19 | 2018-05-22 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七二研究所） | A kind of preparation method of sheet metal lithium base cathode |
| CN109817887A (en) * | 2019-03-19 | 2019-05-28 | 北京航空航天大学 | A kind of high volume energy density lithium metal battery |
| CN109950544A (en) * | 2017-12-21 | 2019-06-28 | 中国科学院上海硅酸盐研究所 | It is a kind of to prepare graphene modified collector and preparation method thereof using plasma auxiliary chemical vapor deposition |
| CN110190286A (en) * | 2019-05-24 | 2019-08-30 | 吉林大学 | A kind of vertical graphene-copper foil composite current collector and preparation method thereof based on growth in situ |
| CN111048750A (en) * | 2019-11-12 | 2020-04-21 | 北京理工大学 | Graphene aerogel/metallic lithium composite negative electrode material and preparation method thereof |
| CN111211292A (en) * | 2019-11-22 | 2020-05-29 | 中国科学院大连化学物理研究所 | Three-dimensional graphene composite lithium alloy cathode, preparation method thereof and application of three-dimensional graphene composite lithium alloy cathode in lithium ion battery |
-
2022
- 2022-03-03 CN CN202210206689.8A patent/CN114566613A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108063218A (en) * | 2017-12-19 | 2018-05-22 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七二研究所） | A kind of preparation method of sheet metal lithium base cathode |
| CN109950544A (en) * | 2017-12-21 | 2019-06-28 | 中国科学院上海硅酸盐研究所 | It is a kind of to prepare graphene modified collector and preparation method thereof using plasma auxiliary chemical vapor deposition |
| CN109817887A (en) * | 2019-03-19 | 2019-05-28 | 北京航空航天大学 | A kind of high volume energy density lithium metal battery |
| CN110190286A (en) * | 2019-05-24 | 2019-08-30 | 吉林大学 | A kind of vertical graphene-copper foil composite current collector and preparation method thereof based on growth in situ |
| CN111048750A (en) * | 2019-11-12 | 2020-04-21 | 北京理工大学 | Graphene aerogel/metallic lithium composite negative electrode material and preparation method thereof |
| CN111211292A (en) * | 2019-11-22 | 2020-05-29 | 中国科学院大连化学物理研究所 | Three-dimensional graphene composite lithium alloy cathode, preparation method thereof and application of three-dimensional graphene composite lithium alloy cathode in lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| QINRU YANG等: "Vertically-oriented graphene nanowalls: Growth and application in Li-ion batteries" * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Interfacial design of dendrite‐free zinc anodes for aqueous zinc‐ion batteries | |
| CN110649267B (en) | Composite metal lithium cathode, preparation method and metal lithium battery | |
| Wang et al. | Infiltrating lithium into carbon cloth decorated with zinc oxide arrays for dendrite-free lithium metal anode | |
| CN106207191B (en) | It is a kind of for improving the efficient negative pole structure of lithium metal battery cycle life | |
| US20200127294A1 (en) | Three-dimensional current collector for metal secondary battery anode, its preparation and application | |
| CN108172761B (en) | Composite negative electrode for lithium secondary battery, and preparation and application thereof | |
| Jiang et al. | In situ growth of CuO submicro-sheets on optimized Cu foam to induce uniform Li deposition and stripping for stable Li metal batteries | |
| CN110010895B (en) | Carbon fiber loaded magnesium oxide particle cross-linked nanosheet array composite material and preparation method and application thereof | |
| CN111048750B (en) | Graphene aerogel/metallic lithium composite negative electrode material and preparation method thereof | |
| CN112768697A (en) | Composite lithium metal negative current collector and preparation method and application thereof | |
| CN107146889B (en) | A kind of graphene/CNTs hybrid does lithium metal battery collector and preparation method thereof | |
| CN109326798B (en) | Preparation method and application of metal lithium negative electrode protection layer | |
| CN111613773A (en) | Composite of glass fiber with hierarchical structure and metallic lithium and preparation method thereof | |
| CN108123141A (en) | A kind of three-dimensional porous foams grapheme material and its application | |
| Gao et al. | Lithiophilic Zn-doped CuO/ZnO nanoarrays modified 3D scaffold inducing lithium lateral plating achieving highly stable lithium metal anode | |
| Tian et al. | Electrodeposition behavior of lithium metal on carbon substrates with surface silvering | |
| CN114373939A (en) | Composite current collector, manufacturing method, pole piece and lithium battery | |
| Kong et al. | Three-dimensional matrix for lithium metal anode for next-generation rechargeable batteries: Structure design and interface engineering | |
| CN114195136A (en) | Preparation method and application of 3D printing nitrogen-doped high-pyrrole graphene aerogel | |
| CN112421115B (en) | Lithium metal-based battery with copper selenide in-situ coated foam copper as lithium metal carrier and preparation method thereof | |
| CN111900373B (en) | Preparation method of lithium dendrite-resistant lithium metal battery cathode side separator material | |
| CN112615004A (en) | Cellulose @ graphene composite carbon aerogel and preparation method and application thereof | |
| CN111710841A (en) | Electro-deposition lithium-carbon-silver composite negative electrode material for lithium battery and preparation method thereof | |
| CN111916671A (en) | Lithium ion battery cathode, lithium ion battery and preparation method of lithium ion battery cathode | |
| CN112216811A (en) | Preparation method of ultrathin lithium metal cathode |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20220531 |