CN117638084A - Lithium negative electrode current collector and preparation method thereof - Google Patents
Lithium negative electrode current collector and preparation method thereof Download PDFInfo
- Publication number
- CN117638084A CN117638084A CN202210952291.9A CN202210952291A CN117638084A CN 117638084 A CN117638084 A CN 117638084A CN 202210952291 A CN202210952291 A CN 202210952291A CN 117638084 A CN117638084 A CN 117638084A
- Authority
- CN
- China
- Prior art keywords
- current collector
- lithium
- bismuth telluride
- substrate
- copper foil
- 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
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 69
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 13
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 49
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000011889 copper foil Substances 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 239000010409 thin film Substances 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 26
- 238000000151 deposition Methods 0.000 claims description 21
- 238000000137 annealing Methods 0.000 claims description 20
- 238000007738 vacuum evaporation Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 27
- 230000008021 deposition Effects 0.000 abstract description 13
- 210000001787 dendrite Anatomy 0.000 abstract description 7
- 238000002715 modification method Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 14
- 238000001704 evaporation Methods 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 150000002641 lithium Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241000949477 Toona ciliata Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a lithium anode current collector, which comprises a current collector substrate and a bismuth telluride thin film layer arranged on the surface of the current collector substrate. According to the invention, the bismuth telluride thin film is modified on the surface of the traditional current collector substrate such as copper foil, so that uniform deposition of lithium ions can be effectively induced, growth of lithium dendrites is avoided, and the coulomb efficiency and the cycle stability of the lithium ion battery are remarkably improved; the related modification method is simple, convenient to operate, short in preparation period and suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of negative electrode materials of metal lithium batteries, and particularly relates to a lithium negative electrode current collector and a preparation method thereof.
Background
The ideal lithium metal negative electrode (lithium negative electrode) has higher theoretical specific capacity (up to 3860 mAh/g), lower oxidation-reduction potential (3.04V relative to a standard hydrogen electrode) and low density, and is expected to be used in the next generation of high energy density batteries; how to achieve uniform and stable lithium deposition is the key to achieving an ideal lithium metal anode.
Uneven deposition of lithium ions can lead to dendritic or mossy dendrite structures on the electrode surface, and can also lead to electrolyte decomposition and gradual aggravation of lithium metal loss, serious decline of coulomb efficiency and shortened cycle life. When lithium dendrites continue to grow until they pierce the separator, thermal runaway and even fire explosion of the battery can also occur, causing serious safety problems. In addition, unlike graphite and silicon cathodes, the relative volume change of metallic lithium cathodes is virtually unlimited, which in turn can lead to collapse of the structure of the electrode during cycling.
To solve the above problems, researchers have developed various methods to stabilize lithium deposition during cycling, such as: and adopting a three-dimensional current collector, modifying a solid electrolyte intermediate phase layer (SEI film), establishing an artificial protection layer or using electrolyte additives and the like. However, the above methods have the problems of complex process and unstable quality, so that there is a need to further explore other materials and methods for simply and efficiently solving the problems of nonuniform deposition of lithium ions in lithium ion batteries.
Disclosure of Invention
Aiming at the problems and the defects existing in the prior art, the invention provides the lithium ion battery negative electrode current collector for realizing uniform deposition of lithium ions, which can effectively improve the coulomb efficiency and the cycle stability of the lithium ion battery; the related preparation method is simpler, has lower cost and is suitable for popularization and application.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a lithium negative electrode current collector comprises a current collector substrate and a bismuth telluride thin film layer arranged on the surface of the current collector substrate.
In the above scheme, the current collector substrate may be a copper substrate or a carbon substrate.
Further, the copper substrate can be copper foil, copper mesh or foam copper; the carbon substrate can be carbon fiber cloth, carbon nano tube or the like.
In the above scheme, the bismuth telluride thin film layer can be P-type bismuth telluride Bi 2-x Sb x Te 3 The film (x takes a value of 0 to 2; preferably 1 to 1.5) or N bismuth telluride Bi 2 Te 3-x Se x The film (x is 0 to 3; preferably 0.1 to 0.5).
In the above scheme, the thermoelectric film layer is formed on the surface of the current collector substrate by vacuum evaporation or magnetron sputtering, and then annealed.
The preparation method of the lithium anode current collector comprises the following steps:
1) Depositing bismuth telluride precursor film on the surface of the current collector substrate by adopting vacuum evaporation or magnetron sputtering technology;
2) And (3) annealing and cooling the product obtained in the step (1) to obtain the lithium negative electrode current collector.
In the scheme, the raw material adopted in the vacuum evaporation process is bismuth telluride powder which is P-type bismuth telluride Bi 2-x Sb x Te 3 Powder (x takes a value of 0 to 2; preferably 1 to 1.5) or bismuth telluride Bi N 2 Te 3-x Se x Powder (x is 0-3; preferably 0.1-0.5), the particle size of the powder is below 120 meshes; the magnetron sputtering process adopts bulk P-type bismuth telluride Bi 2-x Sb x Te 3 Or block N-type bismuth telluride Bi 2 Te 3-x Se x As a target.
Preferably, when the vacuum evaporation process is adopted, the heating time of the bismuth telluride powder is 1-5 min, and the adopted current is 150-200A; the pressure of the vacuum condition is 5×10 -4 ～6×10 -4 Pa。
In the above scheme, the annealing step is performed in a tube furnace.
In the scheme, the annealing step adopts the temperature of 150-250 ℃ and the time of 20-80 min.
In the above scheme, the annealing step is performed under a protective atmosphere such as argon.
The lithium anode is prepared by further depositing the lithium layer on the surface of the lithium anode current collector, so that uniform deposition of lithium ions on the surface of the current collector can be realized, and the coulomb efficiency and the cycle stability of the obtained lithium ion battery can be remarkably improved.
Compared with the prior art, the invention has the beneficial effects that:
1) The invention adopts the current collector with the surface modified bismuth telluride film, can effectively induce the uniform deposition of lithium ions and avoid the growth of lithium dendrites, thereby obviously improving the coulomb efficiency of the lithium ion battery and the cycle stability of the lithium ion battery;
2) The invention adopts a means of film deposition and annealing modification to prepare the bismuth telluride film modified lithium negative electrode current collector, and has simple related process and short preparation period, thereby being suitable for mass production.
Drawings
FIG. 1 is a morphology diagram of a lithium negative electrode current collector (modified copper foil) obtained in example 1 of the present invention;
FIG. 2 is a graph showing the morphology of the lithium negative electrode current collector (modified copper foil) obtained in example 2 of the present invention;
FIG. 3 is a graph showing the X-ray diffraction (XRD) contrast of the lithium negative electrode current collector obtained in example 3 of the invention;
FIG. 4 is a surface microstructure of a lithium negative electrode current collector (modified copper foil) obtained in example 4 of the present invention;
FIG. 5 is a microstructure of lithium deposition of the lithium anode current collector obtained in example 4 of the present invention under DOL/DME as an organic ether electrolyte;
FIG. 6 is a graph showing the cycle coulombic efficiency of the lithium ion battery constructed in example 5 of the present invention versus the lithium ion battery constructed in comparative example in an organic ether electrolyte DOL/DME;
FIG. 7 is a graph showing the microstructure of a lithium deposit obtained by conventional copper foil deposition in a comparative example;
fig. 8 is a graph comparing the cycling coulombic efficiency in an organic ether electrolyte DOL/DME of a lithium ion battery constructed according to example 6 of the present invention and a lithium ion battery constructed according to a comparative example.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the following examples, bismuth telluride powder used was obtained by crushing and grinding a zone-melted bismuth telluride ingot, and the grain size was 120 mesh or less.
Example 1
A lithium negative current collector comprises a copper foil and a film layer, wherein the film layer adopts a vacuum evaporation mode to carry out bismuth Bi telluride on P type 0.5 Sb 1.5 Te 3 The powder is arranged on the surface of a copper foil substrate and then annealed, and the preparation method comprises the following specific steps:
1) Fixing copper foil toOn the base of the vacuum chamber of the vacuum evaporation coating equipment, 0.85g P bismuth telluride Bi is added 0.5 Sb 1.5 Te 3 Uniformly dispersing powder on an evaporation boat and fixing the evaporation boat between two electrodes of a vacuum chamber; vacuumizing to make the pressure of vacuum chamber 6×10 -4 Pa, heating the P-type bismuth telluride Bi under 155A current 0.5 Sb 1.5 Te 3 Powder for 2min, depositing on the surface of the copper foil to obtain a precursor film;
2) And then transferring the lithium anode current collector into a tube furnace, and annealing the lithium anode current collector in an argon atmosphere at the annealing temperature of 250 ℃ for 60min (the heating speed and the cooling speed are 5 ℃/min).
A physical diagram of the lithium anode current collector obtained in the embodiment is shown in fig. 1, and the obtained film layer is gray black.
Example 2
A lithium negative current collector comprises a copper foil and a film layer, wherein the film layer adopts a vacuum evaporation mode to carry out N-type bismuth telluride Bi 2 Te 2.7 Se 0.3 The powder is arranged on the surface of a copper foil substrate and then annealed, and the preparation method comprises the following specific steps:
1) Fixing copper foil on a base of a vacuum chamber of vacuum evaporation coating equipment, and fixing 1.05g N bismuth telluride Bi 2 Te 2.7 Se 0.3 Uniformly dispersing powder on an evaporation boat and fixing the evaporation boat between two electrodes of a vacuum chamber; vacuumizing to make the vacuum chamber maintain the vacuum environment at 5×10 pressure -4 Pa, heating N-type bismuth telluride Bi under 160A current 2 Te 2.7 Se 0.3 Powder for 1min, depositing on the surface of the copper foil to obtain a precursor film;
2) And then transferring the lithium anode current collector into a tube furnace, and annealing the lithium anode current collector in an argon atmosphere at the annealing temperature of 200 ℃ for 60 min.
A physical diagram of the lithium anode current collector obtained in the embodiment is shown in FIG. 2, and the obtained film layer is black.
Example 3
A lithium negative current collector comprises a copper foil and a film layer, wherein the film layer adopts a vacuum evaporation mode to carry out P-type bismuth telluride Bi 0.5 Sb 1.5 Te 3 The powder is arranged on the surface of a copper foil substrate and then annealed, and the preparation method comprises the following specific steps:
1) Fixing copper foil on a base of a vacuum chamber of vacuum evaporation coating equipment, and fixing 0.91g P bismuth telluride Bi 0.5 Sb 1.5 Te 3 Uniformly dispersing powder on an evaporation boat and fixing the evaporation boat between two electrodes of a vacuum chamber; vacuumizing to make the vacuum chamber maintain the vacuum environment at 6×10 pressure -4 Pa, heating P-type bismuth telluride Bi under 158A current 0.5 Sb 1.5 Te 3 Powder for 1min, depositing on the surface of the copper foil to obtain a precursor film;
2) And then transferring the lithium anode current collector into a tube furnace, and annealing the lithium anode current collector in an argon atmosphere at the annealing temperature of 250 ℃ for 60 min.
XRD phase analysis is carried out on the lithium anode current collector obtained by the implementation, the result is shown in figure 3, and the P-type bismuth telluride Bi can be obviously observed in the figure 0.5 Sb 1.5 Te 3 Is a characteristic diffraction peak of (2).
Example 4
A lithium negative current collector comprises a copper foil and a film layer, wherein the film layer adopts a vacuum evaporation mode to carry out bismuth Bi telluride on P type 0.5 Sb 1.5 Te 3 The powder is arranged on the surface of a copper foil substrate and then annealed, and the preparation method comprises the following specific steps:
1) Fixing copper foil on a base of a vacuum chamber of vacuum evaporation coating equipment, and fixing 0.90g P bismuth telluride Bi 0.5 Sb 1.5 Te 3 Uniformly dispersing powder on an evaporation boat and fixing the evaporation boat between two electrodes of a vacuum chamber; vacuumizing to make the vacuum chamber maintain the vacuum environment at 5.5X10 pressure -4 Pa, heating the P-type bismuth telluride Bi under 155A current 0.5 Sb 1.5 Te 3 Powder for 3min, depositing on the surface of the copper foil to obtain a precursor film;
2) And then transferring the lithium anode current collector into a tube furnace, and annealing the lithium anode current collector in an argon atmosphere at the annealing temperature of 250 ℃ for 60 min.
The size of the P-type bismuth telluride grains evaporated is micron-sized as seen by field emission scanning electron microscopy, as shown in fig. 4.
The lithium ion battery cathode obtained in the embodiment is assembled with a 12mm lithium sheet, the electrolyte is organic ether electrolyte DOL/DME, and the diaphragm is a polypropylene diaphragm used by commercial lithium batteries. The battery was allowed to stand for 12 hours and then tested under the current density of 1mA/cm 2 Deposition capacity of 4mAh/cm 2 Lithium of (2); the deposited lithium was gradually smoothed and rounded as observed by field emission scanning electron microscopy, and the result is shown in fig. 5.
Example 5
A lithium negative current collector comprises a copper foil and a film layer, wherein the film layer adopts a vacuum evaporation mode to carry out N-type bismuth telluride Bi 2 Te 2.7 Se 0.3 The powder is arranged on the surface of a copper foil substrate and then annealed, and the preparation method comprises the following specific steps:
1) Fixing copper foil on a base of a vacuum chamber of vacuum evaporation coating equipment, and fixing 0.88. 0.88g N bismuth telluride Bi 2 Te 2.7 Se 0.3 Uniformly dispersing powder on an evaporation boat and fixing the evaporation boat between two electrodes of a vacuum chamber; vacuumizing to make the vacuum chamber maintain the vacuum environment at 5.5X10 pressure -4 Pa, heating N-type bismuth telluride Bi under 160A current 2 Te 2.7 Se 0.3 Powder for 1min, depositing on the surface of the copper foil to obtain a precursor film;
2) And then transferring the material into a tube furnace, and annealing the material in an argon atmosphere at the annealing temperature of 200 ℃ for 60min to obtain the lithium ion battery cathode.
The lithium ion battery cathode obtained in the embodiment is assembled with a 12mm lithium sheet, the electrolyte is organic ether electrolyte DOL/DME, and the diaphragm is a polypropylene diaphragm used by commercial lithium batteries. The cell was tested after 12 hours of standing under the current density of 1mA/cm 2 Capacity of 4mAh/cm 2 The test results are shown in fig. 6.
Example 6
A lithium negative current collector comprises a copper foil and a film layer, wherein the film layer adopts a vacuum evaporation mode to carry out bismuth Bi telluride on P type 0.5 Sb 1.5 Te 3 Powder deviceThe copper foil is obtained by placing the copper foil on the surface of a copper foil substrate and then annealing, and the preparation method comprises the following specific steps:
1) Fixing copper foil on a base of a vacuum chamber of vacuum evaporation coating equipment, and fixing 0.88. 0.88g P bismuth telluride Bi 0.5 Sb 1.5 Te 3 Uniformly dispersing powder on an evaporation boat and fixing the evaporation boat between two electrodes of a vacuum chamber; vacuumizing to make the vacuum chamber maintain the vacuum environment at 5.5X10 pressure -4 Pa, heating the P-type bismuth telluride Bi under 155A current 0.5 Sb 1.5 Te 3 Powder for 1min, depositing on the surface of the copper foil to obtain a precursor film;
2) And then transferring the material into a tube furnace, and annealing the material in an argon atmosphere at the annealing temperature of 250 ℃ for 60min to obtain the lithium ion battery cathode.
The lithium ion battery is assembled with a 12mm lithium sheet, the electrolyte is organic ether electrolyte DOL/DME, and the diaphragm is a polypropylene diaphragm used by a commercial lithium battery. The cell was tested after 12 hours of standing under the current density of 1mA/cm 2 The capacity is 1mAh/cm 2 The test results are shown in fig. 7.
The following compares the battery containing the bismuth telluride thin film layer in the above examples with specific comparative examples, and details the beneficial effects of the negative electrode modifying material provided by the present invention.
Comparative example
Copper foil used in commercial lithium batteries is punched to obtain copper foil with the diameter of 12mm, the copper foil is assembled with a lithium sheet with the diameter of 12mm, electrolyte is organic ether electrolyte DOL/DME, and a diaphragm is a polypropylene diaphragm used in commercial lithium batteries.
Fig. 6 is a graph showing comparison of coulombic efficiencies of lithium ion batteries obtained in example 5 of the present invention and comparative example, and it can be seen that: in the ether electrolyte DOL/DME system, the N-type bismuth telluride Bi described in example 5 is used 2 Te 2.7 Se 0.3 The film layer modified copper foil can effectively avoid growth of lithium dendrite, improves the cycle stability of the lithium ion battery, and has higher coulomb efficiency than that of the lithium ion battery obtained by adopting the traditional copper foil.
FIG. 7 is a graph showing that the battery of the comparative example was tested under the test condition of 1mA/cm 2 At a current density, a deposition capacity of 4mAh/cm 2 The morphology of the lithium negative electrode obtained after lithium was found to lead to dendrite growth of lithium when unmodified copper foil was used as current collector.
Fig. 8 is a graph showing comparison of coulombic efficiencies of lithium ion batteries obtained in example 6 of the present invention and comparative example, and it can be seen that: in the ether electrolyte DOL/DME system, the P-type bismuth telluride Bi described in example 6 is used 0.5 Sb 1.5 Te 3 When the film layer modified copper foil is used as a current collector to deposit a lithium cathode, the growth of lithium dendrite can be effectively avoided, the cycling stability of the lithium ion battery is improved, and the coulomb efficiency is obviously higher than that of a comparative example adopting a traditional copper foil current collector.
The invention is not limited to the embodiments described above, but a number of modifications and adaptations can be made by a person skilled in the art without departing from the principle of the invention, which modifications and adaptations are also considered to be within the scope of the invention. What is not described in detail in this specification is prior art known to those skilled in the art.
Claims (8)
1. The lithium negative electrode current collector is characterized by comprising a current collector substrate and a bismuth telluride thin film layer arranged on the surface of the current collector substrate.
2. The lithium anode current collector of claim 1, wherein the current collector substrate is a copper substrate or a carbon substrate.
3. The lithium anode current collector of claim 2, wherein the copper substrate is copper foil, copper mesh or copper foam; the carbon substrate is carbon fiber cloth or carbon nano tube.
4. The lithium anode current collector of claim 1, wherein the bismuth telluride thin film layer is P-type bismuth telluride Bi 2-x Sb x Te 3 Film or N-type bismuth telluride Bi 2 Te 3-x Se x A film.
5. The lithium anode current collector according to claim 1, wherein the bismuth telluride thin film layer is formed on the surface of the current collector substrate by vacuum evaporation or magnetron sputtering, and then annealed.
6. The method for preparing a lithium anode current collector according to any one of claims 1 to 5, comprising the steps of:
1) Depositing bismuth telluride precursor film on the surface of the current collector substrate by adopting vacuum evaporation or magnetron sputtering technology;
2) And (3) annealing and cooling the product obtained in the step (1) to obtain the lithium negative electrode current collector.
7. The method according to claim 6, wherein the raw material used in the vacuum evaporation process is P-type bismuth telluride Bi 2-x Sb x Te 3 Powder or N-type bismuth telluride Bi 2 Te 3-x Se x Powder with particle size below 120 mesh; the magnetron sputtering process adopts bulk P-type bismuth telluride Bi 2-x Sb x Te 3 Or block N-type bismuth telluride Bi 2 Te 3-x Se x As a target.
8. The method according to claim 6, wherein the annealing step is performed at a temperature of 150 to 250℃for 20 to 80 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210952291.9A CN117638084A (en) | 2022-08-09 | 2022-08-09 | Lithium negative electrode current collector and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210952291.9A CN117638084A (en) | 2022-08-09 | 2022-08-09 | Lithium negative electrode current collector and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117638084A true CN117638084A (en) | 2024-03-01 |
Family
ID=90034310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210952291.9A Pending CN117638084A (en) | 2022-08-09 | 2022-08-09 | Lithium negative electrode current collector and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117638084A (en) |
-
2022
- 2022-08-09 CN CN202210952291.9A patent/CN117638084A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110676420B (en) | Lithium ion battery's lithium diaphragm of mending | |
| CN112421048A (en) | Method for preparing graphite-coated nano-silicon lithium battery negative electrode material at low cost | |
| CN110190240B (en) | Composite lithium oxide film and preparation method and application thereof | |
| CN112875680B (en) | Preparation method of flaky Fe-based alloy catalytic growth carbon nanotube array | |
| CN113479860B (en) | SbPO (styrene-ethylene-propylene-diene monomer) 4 Preparation method of nitrogen-doped carbon composite material | |
| CN111009647A (en) | Lithium borosilicate alloy cathode active material of lithium secondary battery, cathode, preparation and application thereof | |
| CN114122332A (en) | Method for preparing three-dimensional metal lithium cathode by using MOFs (metal-organic frameworks) derivatives | |
| CN111370691B (en) | Lithium ion battery cathode and preparation method thereof | |
| CN116565214A (en) | Modified lithium metal negative electrode current collector and preparation method thereof | |
| CN110783556A (en) | Composite three-dimensional composite structure film and preparation method and application thereof | |
| CN117638084A (en) | Lithium negative electrode current collector and preparation method thereof | |
| CN114914414A (en) | Preparation method of silicon/titanium-niobium oxide composite anode material of lithium ion battery | |
| CN109244384B (en) | Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof | |
| CN112496333A (en) | Preparation method and application of Si-Ti alloy nano powder | |
| CN110923646A (en) | Composite carbon film and preparation method and application thereof | |
| CN113690402B (en) | Lithium ion battery, lithium ion battery cathode and preparation method thereof | |
| CN110581263A (en) | preparation method of manganese dioxide modified lithium-sulfur battery metal lithium cathode and lithium-sulfur battery | |
| CN115360026B (en) | Preparation method of carbon-based composite high-entropy alloy CuAgCoCdZn lithium electrode material | |
| CN114464773B (en) | Composite lithium-rich anode modified by conductive material and preparation method and application thereof | |
| CN115275160B (en) | Carbon-based five-membered high-entropy alloy NiCuZnCdIn material and preparation method and application thereof | |
| CN116666575A (en) | Preparation method and application of silicon-based composite material | |
| CN117039002A (en) | Copper-based current collector and preparation method and application thereof | |
| CN115513412A (en) | Tin-based lithium source composite solid electrode and preparation method and application thereof | |
| CN116613283A (en) | Lithium metal negative electrode and preparation method and application thereof | |
| CN113293376A (en) | LiF/SiOxFilm and preparation method thereof |
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 |