CN109888294A - A kind of preparation method of three-dimensional netted copper current collector - Google Patents
A kind of preparation method of three-dimensional netted copper current collector Download PDFInfo
- Publication number
- CN109888294A CN109888294A CN201910100740.5A CN201910100740A CN109888294A CN 109888294 A CN109888294 A CN 109888294A CN 201910100740 A CN201910100740 A CN 201910100740A CN 109888294 A CN109888294 A CN 109888294A
- Authority
- CN
- China
- Prior art keywords
- copper
- preparation
- fiber
- solution
- spinning
- 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
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
Abstract
The present invention relates to a kind of preparation methods of three-dimensional netted copper current collector, include the following steps: 1) to select polymer polyvinylidene fluoride, polyacrylonitrile, polyethylene glycol oxide, polylactic acid or polyimides as solute, using water or organic solvent as solvent, obtains uniform solution and be used as to spinning solution；2) electrospinning will be carried out to spinning solution, and will obtain the fiber for the tridimensional network that diameter is 100nm~2 μm；3) nanofiber of the resulting tridimensional network of step 2) is roughened, is sensitized and is activated first, the layers of copper for being then 0.1~1 μm in nanofiber surface plating a layer thickness；4) using the fiber after plated copper obtained in step 3) as cathode, using platinum, titanium or stainless steel as anode, copper fiber is obtained in one layers of copper of surface electro-deposition of fiber, the diameter for controlling copper fiber is 1~6 μm；5) copper fiber obtained in step 4) is compacted, is obtained with a thickness of the copper current collector of 8~15 μm of tridimensional network.
Description
Technical field
The present invention relates to a kind of preparation method of negative electrode of lithium ion battery collector more particularly to a kind of three-dimensional netted copper collection
The preparation method of fluid, belongs to technical field of lithium ion.
Background technique
The double challenge that the mankind are faced with fossil resources exhaustion and living environment deteriorates, countries in the world are accelerating to grind
Hair promotes new cleaning fuel.The advantages that lithium ion battery is with its high-energy-density density, relatively high safety, greatly at present
Range is applied in portable electronic device, the fields such as electric car and energy storage.As lithium-ion-power cell, in order to meet
The requirement that electric car constantly promotes course continuation mileage, more stringent requirements are proposed for energy density and high rate performance to battery.
The critical component of lithium ion battery includes anode, cathode, electrolyte, diaphragm and collector.Positive electrode current collector
Aluminium foil is generally used, negative current collector mostly uses copper foil.In order to promote the specific energy density of battery, theoretical energy density is higher
Electrode material is designed developed, while collector thinner, that quality is lighter gradually becomes trend.Designing one kind has
On the one hand negative electrode material can directly be filled in reticulated collectors, significantly be promoted by the copper current collector of tridimensional network
The energy density of battery；On the other hand, copper current collector is combined into one with negative electrode material, accomplishes negative electrode material and three-dimensional netted copper parent
Contiguity touching, can effectively promote the high rate performance of battery.
Application No. is 201810739579.1 Chinese patent applications to disclose a kind of three-dimensional hybrid ion-electron conductor collection
Fluid and preparation method thereof, preparation method are as follows: (1) precursor solution is prepared: will be used to form the polyphosphazene polymer of electronic conductor
It closes object, be used to form the metal salt of ion conductor and complexing agent is dissolved in solvent, stirring is until obtain uniform solution；The high score
Sub- polymer is polyvinyl alcohol, polyvinylpyrrolidone or polyacrylonitrile, concentration in precursor solution is 0.05~
0.20kg/L；The metal salt is the metal salt for being capable of forming LLZO, LLTO or LATP nano-ceramic particle, and the metal salt exists
Concentration in precursor solution can stoichiometrically be scaled LLZO, LLTO or LATP nanometer of 0.05~0.15mol/L
Ceramic particle；The complexing agent is citric acid, and the concentration in precursor solution is 0.10~0.30mol/L；(2) Static Spinning
Silk: the static spinning membrane that the precursor solution that step (1) is prepared passes through electrostatic spinning machine preparation insulation；(3) high-temperature calcination: will
The static spinning membrane that step (2) obtains pre-oxidizes 3~5h, 1~5 DEG C/min of heating rate in 180~250 DEG C of air；Exist afterwards
3~5h is calcined in 800~1000 DEG C of protection gas, 5~10 DEG C/min of heating rate obtains three-dimensional hybrid after being fully crystallized, being carbonized
Ion-electron conductor collector.Be used to form in this method the metal salt of ion conductor during electrostatic spinning by atom,
Intermolecular attraction is adsorbed on the static spinning membrane of three-dimensional structure, the netted afflux of three-dimensional structure in high-temperature burning process
Body structure crystalline, carbonization, the metal salt for being used to form ion conductor are oxidized generation ceramic oxide, although resulting three-dimensional mixed
Closing ion-electron conductor collector makes lithium an- ode in high capacity (20mAhcm-2), high current density (5mA cm-2) under can
Long-time stable circulation, but its toughness and tensile strength wretched insufficiency, can not effectively fill electrode material, it is even more impossible to be compacted,
The serialization of lithium ion battery production process is not can guarantee.
Summary of the invention
The present invention provides a kind of three-dimensional netted copper for deficiency present in existing negative electrode of lithium ion battery copper current collector
The preparation method of collector.
The technical scheme to solve the above technical problems is that
A kind of preparation method of three-dimensional netted copper current collector, includes the following steps:
1) preparation of precursor solution: select polymer polyvinylidene fluoride, polyacrylonitrile, polyethylene glycol oxide, polylactic acid or
Polyimides is as solute, using water or organic solvent as solvent, is uniformly mixed to obtain uniform solution as molten to spinning
Liquid；
2) electrostatic spinning: will carry out electrospinning to spinning solution, obtain the tridimensional network that diameter is 100nm~2 μm
Nanofiber；
3) electroless copper: the nanofiber of the resulting tridimensional network of step 2) is roughened, is sensitized and is lived first
Change, the layers of copper for being then 0.1~1 μm in nanofiber surface plating a layer thickness；
4) electro-coppering: using the fiber after plated copper obtained in step 3) as cathode, using platinum, titanium or stainless steel as
Anode obtains copper fiber in one layers of copper of surface electro-deposition of fiber, and the diameter for controlling copper fiber is 1~6 μm；
5) it is compacted: copper fiber obtained in step 4) is compacted, obtain the tridimensional network that actual (real) thickness is 8~15 μm
Copper current collector.
Further, the step 2) electrostatic spinning adds high pressure as 10~50kV, and spinning capillary inner diameter is 0.1~2mm,
Receiving distance is 3~25mm.
Further, the technological parameter of the step 4) electrodeposition process are as follows: Cu2+45~60g/L, H2SO450~80g/L,
Cl-3~8ppm of 20~30ppm, brightener sodium polydithio-dipropyl sulfonate SPS or collagen, 45~50 DEG C of temperature, electric current is close
Spend 2~5A/dm2。
Further, SnCl is respectively adopted in step 3)2Solution and PdCl2Solution to the nanofiber of tridimensional network into
Row sensitization and activation.
Further, organic solvent described in step 1) is polyalcohol, acetone, dimethylformamide, dimethyl acetamide, two
Any one in methyl sulfoxide.
It further, is 20~25wt% to the concentration of spinning solution described in step 1).
The beneficial effects of the present invention are:
1) on the one hand the three-dimensional netted skeleton of copper current collector is provided by the method for electrostatic spinning, on the other hand can changed
The intensity of kind copper current collector；It is certain thickness in the surface of three-dimensional reticular fiber deposition by chemical plating, the method for electrochemical plating
Layers of copper, has really been made the copper current collector with three-dimensional intercommunication reticular structure, and to punch copper foil as if collector, only
It can accomplish the intercommunication of upper and lower surface, can not accomplish three-dimensional intercommunication；
2) after being simply compacted, electrode material is filled in three-dimensional netted copper current collector, provided by the invention three-dimensional netted
The thickness that the thickness of copper current collector is substantially equal to copper foil adds the thickness of electrode material, has really accomplished collector and electrode
The fusion of material, while energy density is promoted, the high rate performance of battery can also be greatly improved；
3) using the netted copper current collector tensile strength with higher of this method preparation, it can be ensured that in netted copper afflux
Serialization in production procedure and lithium ion battery production process；
4) there is certain toughness using the netted copper current collector of this method preparation, a degree of compacting can be carried out,
There is apparent advantage compared with netted inorganic ceramic class collector.
Specific embodiment
Principles and features of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
Embodiment 1:
A method of preparing three-dimensional netted copper current collector, comprising the following steps:
1) polyacrylonitrile being dissolved in dimethylformamide, then stirring and dissolving 2.5h stirs 10h at 60 DEG C, until
Solution stable homogeneous, obtaining concentration is 20wt% to spinning solution；
2) electrospinning will be carried out to spinning solution, and will obtain the three-dimensional netted polyacrylonitrile fibre that diameter is 500nm or so, wherein
Electrospinning conditions are as follows: voltage 25kV, spinning capillary inner diameter 0.25mm, receiving distance is 15mm；
3) the resulting polyacrylonitrile fibre of step 2) is roughened, SnCl is then respectively adopted2Solution and PdCl2Solution
It is sensitized and is activated, sink upper 0.3 μm or so of copper coating on polyacrylonitrile fibre surface with the method for electroless copper；
4) Cu is prepared2+45g/L, H2SO420ppm Cl is added in the sour copper electrolyte of 50g/L thereto-It is (poly- with 5ppm SPS
Two sulphur, two propane sulfonic acid sodium), controlled at 50 DEG C, using titanium plate as anode, fiber made from step 3) is cathode, in 2A/dm2
45s is deposited under current density, obtains the three-dimensional netted copper fiber that diameter is 2.4 μm；
5) copper fiber obtained in step 4) is compacted obtain three-dimensional netted copper current collector, after compacting with a thickness of
10μm。
Embodiment 2:
A method of preparing three-dimensional netted copper current collector, comprising the following steps:
1) Kynoar being dissolved in dimethyl sulfoxide, then stirring and dissolving 2.5h stirs 10h at 60 DEG C, until
Solution stable homogeneous, obtain 25wt% to spinning solution；
2) electrospinning will be carried out to spinning solution, and will obtain the three-dimensional netted polyvinylidene fluoride that diameter is 900nm or so,
Middle electrospinning conditions are as follows: voltage 20kV, spinning capillary inner diameter 2.0mm, receiving distance is 3mm；
3) polyvinylidene fluoride in step 2) is roughened, SnCl is then respectively adopted2Solution and PdCl2Solution
It is sensitized and is activated, sink upper 0.1 μm or so of copper coating on polyvinylidene fluoride surface with the method for electroless copper；
4) Cu is prepared2+45g/L, H2SO420ppm Cl is added in the sour copper electrolyte of 50g/L thereto-, 5ppm SPS, control
Temperature processed is 50 DEG C；Using titanium plate as anode, copper fiber made from step 3) is cathode, in 2A/dm245s is deposited under current density,
Obtain the three-dimensional netted copper fiber that diameter is 4.2 μm；
5) copper fiber in step 4) is compacted obtain three-dimensional netted copper current collector, with a thickness of 10 μ after compacting
m。
Embodiment 3:
A method of preparing three-dimensional netted copper current collector, comprising the following steps:
1) polylactic acid is dissolved in acetone, then stirring and dissolving 2.5h stirs 10h at 40 DEG C, until solution is uniform steady
It is fixed, obtain 20wt% to spinning solution；
2) electrospinning will be carried out to spinning solution, and will obtain the three-dimensional netted acid fiber by polylactic that diameter is 1 μm or so；Wherein electrostatic
Spinning condition are as follows: voltage 10kV, spinning capillary inner diameter 0.10mm, receiving distance is 20mm；
3) acid fiber by polylactic obtained in step 2) is roughened, SnCl is then respectively adopted2Solution and PdCl2Solution
It is sensitized and is activated, sink upper 1.0 μm or so of copper coating in polylactic acid fiber surface with the method for electroless copper；
4) Cu is prepared2+45g/L, H2SO420ppm Cl is added in the sour copper electrolyte of 50g/L-, 8ppm SPS, control temperature
It is 50 DEG C；Using titanium plate as anode, copper fiber made from step 3) is cathode, in 5A/dm230s is deposited under current density, is obtained straight
The three-dimensional netted copper fiber that diameter is 3.6 μm；
5) the resulting copper fiber of step 4) is compacted obtain three-dimensional netted copper current collector, with a thickness of 10 after compacting
μm。
Embodiment 4:
A method of preparing three-dimensional netted copper current collector, comprising the following steps:
1) polyethylene glycol oxide is dissolved in distilled water, then stirring and dissolving 2.5h stirs 10h at 60 DEG C, until solution
Stable homogeneous, obtaining concentration is 25wt% to spinning solution；
2) electrospinning will be carried out to spinning solution, and will obtain the three-dimensional netted polyethylene glycol oxide fiber that diameter is 2 μm or so；Wherein
Electrospinning conditions are as follows: voltage 25kV, spinning capillary inner diameter 0.25mm, receiving distance is 25mm；
3) polyethylene glycol oxide fiber obtained in step 2) is roughened, SnCl is then respectively adopted2Solution and PdCl2
Solution is sensitized and is activated；Upper 0.5 μm or so of copper coating is sunk in polyethylene glycol oxide fiber surface with the method for electroless copper；
4) Cu is prepared2+60g/L, H2SO430ppm Cl is added in the sour copper electrolyte of 80g/L thereto-With 5ppm collagen egg
White powder, controlled at 45 DEG C, using titanium plate as anode, copper fiber made from step 3) is cathode, in 3A/dm2Current density
Lower deposition 60s obtains the three-dimensional netted copper fiber that diameter is 6 μm；
5) copper fiber in step 4) is compacted obtain three-dimensional netted copper current collector, with a thickness of 15 μ after compacting
m。
Embodiment 5:
A method of preparing three-dimensional netted copper current collector, comprising the following steps:
1) soluble polyimide is dissolved in dimethyl acetamide, then stirring and dissolving 2.5h is stirred at 60 DEG C
20h, until solution stable homogeneous, obtain 20wt% to spinning solution；
2) electrospinning will be carried out to spinning solution, and will obtain the three-dimensional netted polyimide fiber that diameter is 100nm or so；Wherein
Electrospinning conditions are as follows: voltage 50kV, spinning capillary inner diameter 0.75mm, receiving distance is 10mm；
3) polyimide fiber obtained in step 2) is roughened, SnCl is then respectively adopted2Solution and PdCl2It is molten
Liquid is sensitized and is activated, and sinks upper 0.4 μm or so of copper coating on polyimide fiber surface with the method for electroless copper；
4) Cu is prepared2+45g/L, H2SO420ppm Cl is added in the sour copper electrolyte of 50g/L thereto-, 5ppm SPS, control
Temperature processed is 50 DEG C；Using titanium plate as anode, copper fiber made from step 3) is cathode, in 2A/dm2Current density under deposit
45s obtains the three-dimensional netted copper fiber that diameter is 1 μm.
5) copper fiber in step 4) is compacted obtain three-dimensional netted copper current collector, 8 μm of compacted thickness.
Comparative example 1:
(1) by the polyvinyl alcohol of 0.05kg/L concentration, the LiAc2H of 1.05mol/L concentration2O, 0.45mol/L concentration
LaAc3·xH2O, the ZrAc of 0.30mol/L concentration4It is dissolved in 20mL deionized water with the anhydrous citric acid of 0.30mol/L concentration,
Stirring to obtain uniform solution；
(2) static spinning membrane that electrostatic spinning is insulated is carried out using above-mentioned solution, wherein spinning voltage is 20kV, note
It is 0.40ml/h that emitter syringe needle, which injects speed, and syringe needle to the distance between aluminium foil receiver is 20cm, and the spinning time is 2h；
(3) above-mentioned static spinning membrane is placed in Muffle furnace, is pre-oxidized in air atmosphere, wherein temperature is 180
DEG C, time 5h, heating rate is 1 DEG C/min；
(4) above-mentioned pre-oxidation film is placed in tube furnace, carries out high-temperature calcination in the case where protecting gas atmosphere, wherein temperature is
800 DEG C, time 3h, heating rate is 5 DEG C/min, is obtained with a thickness of the collector of 100 μm of three-dimensional fiber network structures.
Examples 1 to 5 and the resulting three-dimensional netted copper current collector of comparative example 1 are tested for the property, as a result such as 1 institute of table
Show.
Table 1: the performance test data of three-dimensional netted copper current collector obtained by Examples 1 to 5
| Number | Mass area ratio g/cm2 | Tensile strength/Mpa |
| Embodiment 1 | 42 | 278 |
| Embodiment 2 | 62 | 346 |
| Embodiment 3 | 56 | 335 |
| Embodiment 4 | 72 | 364 |
| Embodiment 5 | 34 | 284 |
| Comparative example 1 | 64 | It is low, it is unable to test |
Using the resulting three-dimensional netted copper current collector of Examples 1 to 5 and common 8 μm of copper foils as negative current collector, with
Graphite is negative electrode material, and LiFePO4 is positive electrode, is prepared into lithium ion battery and carries out the cycle performance of battery and forthright again
It can test, the results are shown in Table 2.Wherein cycle performance is the energy conservation rate after recycling 500 times, and high rate performance is 10C multiplying power
Under charge-discharge energy conservation rate.
Table 2: battery performance test data made from copper current collector obtained by Examples 1 to 5 and common 8 μm of copper foils
| Number | Cycle performance % | High rate performance % |
| Embodiment 1 | 94.8 | 94.3 |
| Embodiment 2 | 95.4 | 95.6 |
| Embodiment 3 | 94.6 | 94.6 |
| Embodiment 4 | 95.1 | 93.7 |
| Embodiment 5 | 94.5 | 95.8 |
| Common copper foil | 92.3 | 76.4 |
By the test data in table 2 it is found that the copper afflux for the tridimensional network being prepared using method of the invention
Body is superior to common copper foil as the resulting lithium ion battery of negative current collector, cycle performance and high rate performance, especially again
Rate performance boost is obvious.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of three-dimensional netted copper current collector, which comprises the steps of:
1) polymer polyvinylidene fluoride, polyacrylonitrile, polyethylene glycol oxide, polylactic acid or polyamides the preparation of precursor solution: are selected
Imines is as solute, using water or organic solvent as solvent, is uniformly mixed to obtain uniform solution as to spinning solution；
2) electrostatic spinning: will carry out electrospinning to spinning solution, obtain the nanometer for the tridimensional network that diameter is 100nm~2 μm
Fiber；
3) electroless copper: the nanofiber of the resulting tridimensional network of step 2) is roughened, is sensitized and is activated first, so
The layers of copper for being afterwards 0.1~1 μm in nanofiber surface plating a layer thickness；
4) electro-coppering: using the fiber after plated copper obtained in step 3) as cathode, using platinum, titanium or stainless steel as sun
Pole obtains copper fiber in one layers of copper of surface electro-deposition of fiber, and the diameter for controlling copper fiber is 1~6 μm；
5) it is compacted: copper fiber obtained in step 4) is compacted, obtain the copper collection for the tridimensional network that actual (real) thickness is 8~15 μm
Fluid.
2. preparation method according to claim 1, which is characterized in that the electrostatic spinning step adds high pressure as 10~
50kV, spinning capillary inner diameter are 0.1~2mm, and receiving distance is 3~25mm.
3. preparation method according to claim 1 or 2, which is characterized in that the technique of the step 4) electrodeposition process is joined
Number are as follows: Cu2+45~60g/L, H2SO450~80g/L, Cl-20~30ppm, brightener sodium polydithio-dipropyl sulfonate SPS or
3~8ppm of collagen, 45~50 DEG C of temperature, 2~5A/dm of current density2。
4. preparation method according to claim 1 or 2, which is characterized in that SnCl is respectively adopted in step 3)2Solution and
PdCl2Solution is sensitized and is activated to the nanofiber of tridimensional network.
5. preparation method according to claim 3, which is characterized in that SnCl is respectively adopted in step 3)2Solution and PdCl2
Solution is sensitized and is activated to the nanofiber of tridimensional network.
6. preparation method according to claim 1 or 2, which is characterized in that organic solvent described in step 1) be polyalcohol,
Acetone, dimethylformamide, dimethyl acetamide, any one in dimethyl sulfoxide.
7. preparation method according to claim 3, which is characterized in that organic solvent described in step 1) is polyalcohol, third
Ketone, dimethylformamide, dimethyl acetamide, any one in dimethyl sulfoxide.
8. the preparation method according to claim 4, which is characterized in that organic solvent described in step 1) is polyalcohol, third
Ketone, dimethylformamide, dimethyl acetamide, any one in dimethyl sulfoxide.
9. preparation method according to claim 5, which is characterized in that organic solvent described in step 1) is polyalcohol, third
Ketone, dimethylformamide, dimethyl acetamide, any one in dimethyl sulfoxide.
10. preparation method described according to claim 1~any one of 9, which is characterized in that molten to spinning described in step 1)
The concentration of liquid is 20~25wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910100740.5A CN109888294A (en) | 2019-01-31 | 2019-01-31 | A kind of preparation method of three-dimensional netted copper current collector |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910100740.5A CN109888294A (en) | 2019-01-31 | 2019-01-31 | A kind of preparation method of three-dimensional netted copper current collector |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109888294A true CN109888294A (en) | 2019-06-14 |
Family
ID=66927528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910100740.5A Pending CN109888294A (en) | 2019-01-31 | 2019-01-31 | A kind of preparation method of three-dimensional netted copper current collector |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109888294A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105350045A (en) * | 2015-10-30 | 2016-02-24 | 浙江理工大学 | Preparing method of electro-coppering conductive fiber |
| CN108011108A (en) * | 2017-11-09 | 2018-05-08 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of the lithium ion battery containing porous copper foil |
| CN108666580A (en) * | 2018-04-13 | 2018-10-16 | 北京卫蓝新能源科技有限公司 | A kind of polymer three-dimensional collector, preparation method and application |
-
2019
- 2019-01-31 CN CN201910100740.5A patent/CN109888294A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105350045A (en) * | 2015-10-30 | 2016-02-24 | 浙江理工大学 | Preparing method of electro-coppering conductive fiber |
| CN108011108A (en) * | 2017-11-09 | 2018-05-08 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of the lithium ion battery containing porous copper foil |
| CN108666580A (en) * | 2018-04-13 | 2018-10-16 | 北京卫蓝新能源科技有限公司 | A kind of polymer three-dimensional collector, preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107681142B (en) | Molybdenum disulfide coated carbon nanofiber used as lithium ion battery negative electrode material and preparation method thereof | |
| CN110690420B (en) | Composite material cathode, battery and preparation method thereof | |
| CN108321376A (en) | A kind of N doping porous carbon nanofiber@tin dioxide lithium ion battery negative pole materials and preparation method thereof | |
| CN109802129B (en) | Metal sodium battery negative electrode material and preparation method and application thereof | |
| CN108682802A (en) | A method of preparing lithium cell negative pole shell-core structure nanofiber | |
| CN106784745A (en) | The sodium-ion battery method for manufacturing electric spinning of cobaltosic oxide carbon nano-fiber | |
| CN112670507A (en) | Preparation method of lithium-sulfur battery intermediate layer of metal selenide-loaded carbon nanofiber and lithium-sulfur battery | |
| CN113564752A (en) | Hollow porous carbon nanofiber with tin oxide loaded on inner tube wall and preparation method and application thereof | |
| CN109817986A (en) | A kind of preparation method of the lithium ion battery based on three-dimensional netted copper current collector | |
| CN108808008A (en) | A kind of three-dimensional hybrid ion-electron conductor collector and its preparation method and application | |
| CN113270275B (en) | Composite electrode derived from metal organic framework and nanofiber and preparation method thereof | |
| CN113921768A (en) | Preparation method of flexible self-supporting iron-doped porous carbon nanofiber lithium metal negative electrode framework material | |
| CN106025274A (en) | ZnFe2O4 porous nanotube negative electrode material for lithium ion battery and electrostatic spinning preparation method thereof | |
| CN108832081A (en) | A kind of preparation method for the composition metal cathode of lithium making lithium metal cross growth | |
| CN109449008B (en) | Preparation method and application of self-supporting hollow core-shell structure electrode material | |
| CN116845348A (en) | Nanogel electrolyte of flexible three-dimensional network and preparation method and application thereof | |
| CN109888294A (en) | A kind of preparation method of three-dimensional netted copper current collector | |
| Zhu et al. | Recognizing the nitrogen/oxygen co-doped lithiophilicity chemistry toward molten Li infusion for fabricating composite Li metal anode | |
| CN113690546A (en) | Lithium-sulfur battery diaphragm and preparation method and application thereof | |
| CN114068872A (en) | Polymer nanofiber metal lithium composite negative electrode with double lithium affinity and preparation method thereof | |
| CN111933866A (en) | Lithium metal battery, interlayer thereof and preparation method | |
| CN116315446A (en) | Sustained-release functional diaphragm and preparation method thereof | |
| CN113471399B (en) | Preparation method and application of high-conductivity Si/C nano-film | |
| CN109390643A (en) | A kind of three-diemsnional electrode heating means being cold-started at low temperature for battery | |
| CN114335427B (en) | Three-dimensional V 2 O 3 Carbon nanofiber composite flexible electrode and preparation method and application 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190614 |
|
| RJ01 | Rejection of invention patent application after publication |