CN114914427A - Self-supporting negative electrode material, preparation method thereof, negative electrode plate and secondary battery - Google Patents
Self-supporting negative electrode material, preparation method thereof, negative electrode plate and secondary battery Download PDFInfo
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Abstract
The invention belongs to the technical field of secondary batteries, and particularly relates to a self-supporting negative electrode material, a preparation method thereof, a negative electrode plate and a secondary battery, wherein the method comprises the following steps: step S1, mixing hydrochloric acid and lithium fluoride, adding MAX phase materials for reaction, adjusting the pH value, ultrasonically stirring, centrifuging to obtain MXene dispersion liquid, cooling and storing; step S2, adding Prussian blue analogue and dispersant into MXene dispersion liquid, mixing and stirring, standing, performing suction filtration, and performing freeze drying to obtain a precursor; and step S3, heating, calcining and oxidizing the precursor to obtain the self-supporting negative electrode material. The invention relates to a preparation method of a self-supporting negative electrode material, which is characterized in that MAX phase materials and Prussian analogues are compounded to prepare the self-supporting negative electrode material which has high conductivity, high reversible specific capacity and difficult lithium precipitation.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a self-supporting negative electrode material, a preparation method thereof, a negative electrode sheet and a secondary battery.
Background
Lithium ion batteries are the most common secondary batteries at present, but in the field of commercial batteries, there has been no great difference in the types of positive and negative electrode materials for over a decade, particularly in graphite as a negative electrode. Nowadays, with the development of science and technology and the improvement of market demand, conventional graphite gradually touches the bottleneck, for example, the application of high voltage lithium cobaltate often leads to the situation of lithium precipitation.
Therefore, a solution to the above-mentioned problems is needed.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the MAX phase material and the Prussian analogue are compounded to prepare the self-supporting negative electrode material which has high conductivity, high reversible specific capacity and difficult lithium precipitation.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a self-supporting negative electrode material comprises the following steps:
step S1, mixing hydrochloric acid and lithium fluoride, adding MAX phase materials for reaction, adjusting the pH value, ultrasonically stirring, centrifuging to obtain MXene dispersion liquid, cooling and storing;
step S2, adding Prussian blue analogue and dispersant into MXene dispersion liquid, mixing and stirring, standing, performing suction filtration, and performing freeze drying to obtain a precursor;
and step S3, heating, calcining and oxidizing the precursor to obtain the self-supporting negative electrode material.
According to the preparation method of the self-supporting cathode material, hydrochloric acid and lithium fluoride are mixed to prepare hydrofluoric acid, the concentration of the hydrofluoric acid is adjustable, and the MAX phase material is etched more accurately. The etched MAX phase material is changed into MXene dispersion liquid, and the MXene dispersion liquid is cooled and stored, so that an accordion-like structure in the MXene dispersion liquid is effectively reserved, the MXene dispersion liquid has a wide specific surface area, sufficient active sites are provided for electrochemical reaction, and subsequent combination with metal is facilitated. The Prussian salt analogue has good conductivity, the MXene dispersion liquid, the Prussian salt analogue and the dispersing agent are mixed and reacted to obtain a precursor, the precursor is heated and calcined to obtain the self-supporting negative electrode material, and the prepared self-supporting negative electrode material has high conductivity and high reversible specific capacity.
The hydrofluoric acid has rigorous preservation conditions and strong corrosivity, is difficult to use directly, and the in-situ growth is favorable for ensuring the quality of the hydrofluoric acid in use and controlling the reaction speed. The hydrochloric acid and the lithium fluoride are mixed to prepare the self-made hydrofluoric acid, and the obtained hydrofluoric acid has adjustable concentration and good controllability and can be adjusted according to the reaction condition. The reaction of the MAX phase material with hydrofluoric acid is as follows:
M n+1 AlX n +3HF→M n+1 X n +AlF 3 +1.5H 2 。
MAX phase materials include Ti 2 AlC、Mo 3 AlC 2 、Ti 3 AlN 2 、Ni 2 One or more of SiC. MAX phase material refers to carbide or nitride with three-layer structure, and its general formula is M n+1 AX n Where M represents a transition metal oxide, A represents an interphase layer, typically an element of the third or fourth main group, usually Al and Si, and X represents nitrogen or carbon. The MAX phase material stacked in such a unit of three layers is removed by acid etching of the intermediate layer a to obtain the accordion-like MXene material as in fig. 2. Preferably, the MAX phase material uses Ti 2 AlC。
The Prussian salt analogue is prepared from a transition metal salt and an organic ligand. Transition metal salts include, but are not limited to, those of Ni, Co, Mn, Fe, Mg, ZnA nitrate or halide salt of one or more metals. Dispersants include, but are not limited to, one or more of trisodium citrate, polyacrylic acid, sodium lauryl sulfate. The organic ligand is one or two of potassium nickel tetrahydride and dimethyl imidazole. Preferably, the chemical reaction formula of the complex between the metal salt and the complexing ligand is that between nickel chloride and potassium nickel tetrahydroformate: 2NiCl 2 +K 4 [Ni(CN) 4 ]→Ni 2 [Ni(CN) 4 ]+4 KCL. The prepared Prussian blue analogue has good electrical property.
Preferably, in the step S1, the concentration of the hydrochloric acid is 5-10 mol/L, the volume is 5-25 ml, the mass of the lithium fluoride is 0.2-15 g, and the mass of the MAX phase material is 0.1-5 g. The concentration and volume of the hydrochloric acid are adjusted, and the amount of generated hydrofluoric acid can be adjusted, so that the etching rate and the etching depth can be adjusted. Preferably, the mass of hydrochloric acid used is 3.285 x 10-3 g, the mass of lithium fluoride is 0.8g, and the mass of MAX phase material is 0.1-3 g, 0.2-3 g, 0.3-3 g, 0.1-0.8 g, 0.5g, 0.6g, 0.7g, 0.8 g. The lithium fluoride has a mass of 0.2 to 10g, 0.2 to 8g, 0.5 to 6g, 0.6g, 0.8g, 1.0g, 1.2g, 1.5g, 2g, 4g, 6 g.
Preferably, in the step S1, the reaction time is 20-30 hours, the pH value is 5-7, the ultrasonic stirring time is 0.5-3 hours, the centrifugation time is 1-10 minutes, and the centrifugation rotating speed is 3000-5000 rpm/min. In step S1, the reaction time is 20 to 28 hours, 22 to 28 hours, 24 to 28 hours, 21 to 25 hours, specifically, the reaction time is 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, the ph is 5, 6, 7, the ultrasonic stirring time is 0.5 hour, 1 hour, 2 hours, 3 hours, and the centrifugation time is 1 minute, 3 minutes, 6 minutes, 8 minutes, 10 minutes. The centrifugation speeds were 3000rpm/min, 3400rpm/min, 3600rpm/min, 3800rpm/min, 4000rpm/min, 4200rpm/min, 4600rpm/min, 4700rpm/min, 4900rpm/min, 5000 rpm/min.
Preferably, the weight parts of the MXene dispersion liquid, the Prussian analogue and the dispersing agent in the step S2 are 4-10: 2-6: 1-2. In the step S2, the weight parts of the MXene dispersion liquid, the Prussian analogue and the dispersing agent are 5-10: 3-6: 1.5-2, 4-10: 4-6: 1.5-2, and 4-10: 5-6: 1-2.
Preferably, the aperture of the suction filtration in the step S2 is 30-50 μm, and the freeze drying time is 10-20 hours. The pore diameter of the filter was 30 μm, 35 μm, 38 μm, 40 μm, 43 μm, 46 μm, 48 μm, and 50 μm, and the freeze-drying time was 10 hours, 12 hours, 14 hours, 15 hours, 16 hours, 18 hours, and 20 hours.
Preferably, the heating and calcining temperature in the step S3 is 350-600 ℃, and the calcining time is 3-6 hours. The temperature of the heating and calcining is 350 ℃, 380 ℃, 400 ℃, 430 ℃, 450 ℃, 480 ℃, 500 ℃, 530 ℃, 550 ℃, 580 ℃ and 600 ℃. The calcination time was 3 hours, 4 hours, 5 hours, and 6 hours.
The second purpose of the invention is: aiming at the defects of the prior art, the self-supporting material is provided, and has the advantages of high porosity and high specific surface.
In order to achieve the purpose, the invention adopts the following technical scheme:
a self-supporting material is obtained by the preparation method of the self-supporting negative electrode material.
Preferably, the thickness of the self-supporting material is 0.01-2 mm. Preferably, the thickness of the self-supporting material is 0.01mm, 0.05mm, 0.1mm, 0.6mm, 1.2mm, 1.7mm, 2 mm.
The third purpose of the invention is that: aiming at the defects of the prior art, the negative plate is provided, has more specific surface area, provides sufficient active sites, and has high specific capacity and strong chemical stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a negative plate is the self-supporting material.
The fourth purpose of the invention is that: aiming at the defects of the prior art, the secondary battery is provided, and has higher reversible specific capacity and good cyclicity.
In order to achieve the purpose, the invention adopts the following technical scheme:
a secondary battery comprises the negative plate.
The secondary battery of the present invention has good rate capability and energy density. The secondary battery comprises a positive plate, an isolating membrane, a negative plate, electrolyte and a shell, wherein the positive plate and the negative plate are separated by the isolating membrane, and the shell is used for packaging the positive plate, the isolating membrane, the negative plate and the electrolyte.
The positive plate comprises a positive current collector and a positive active material layer arranged on at least one surface of the positive current collector, the positive active material layer comprises a positive active material, and the positive active material can be a chemical formula including but not limited to Li a Ni x Co y M z O 2-b N b (wherein a is more than or equal to 0.95 and less than or equal to 1.2, x>0, y is more than or equal to 0, z is more than or equal to 0, and x + y + z is 1,0 is more than or equal to b and less than or equal to 1, M is selected from one or more of Mn and Al and N is selected from F, P, S), and the positive active material can also be selected from the group consisting of but not limited to LiCoO 2 、LiNiO 2 、LiVO 2 、LiCrO 2 、LiMn 2 O 4 、LiCoMnO 4 、Li 2 NiMn 3 O 8 、LiNi 0.5 Mn 1.5 O 4 、LiCoPO 4 、LiMnPO 4 、LiFePO 4 、LiNiPO 4 、LiCoFSO 4 、CuS 2 、FeS 2 、MoS 2 、NiS、TiS 2 And the like. The positive electrode active material may be further modified, and the method of modifying the positive electrode active material is known to those skilled in the art, for example, the positive electrode active material may be modified by coating, doping, and the like, and the material used in the modification may be one or a combination of more of Al, B, P, Zr, Si, Ti, Ge, Sn, Mg, Ce, W, and the like. The positive electrode current collector is generally a structure or part for collecting current, and the positive electrode current collector may be any material suitable for use as a positive electrode current collector of a lithium ion battery in the art, for example, the positive electrode current collector may include, but is not limited to, a metal foil, and the like, and more specifically, may include, but is not limited to, a metal foilAluminum foil, and the like. The dispersant in the positive electrode is polyacrylonitrile or polystyrene.
The positive electrode active material layer further includes a conductive agent, which may be a carbon material, a metal-based material, a conductive polymer, or the like, and any conductive material may be used as the conductive agent as long as it does not cause chemical changes within the battery. Examples of the conductive agent include carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fibers, carbon nanotubes, graphene, or the like; a metal-based material comprising metal powder or metal fibers containing one or more of copper, nickel, aluminum, or silver; conductive polymers such as polyphenylene derivatives; or mixtures thereof.
The positive electrode active material layer further includes a binder, which may be used to improve the binding properties of the positive electrode active materials to each other and to the current collector. Examples of the binder include one or more of synthetic rubber, a polymer material, and the like. Examples of the synthetic rubber include styrene-butadiene-based rubber, fluorine-based rubber, or ethylene propylene diene rubber. The binder may further include, but is not limited to: polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxymethyl methyl cellulose, hydroxydiacetyl cellulose, polyvinyl chloride, carboxy polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymers, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, and the like.
The material of the shell is one of stainless steel and an aluminum plastic film, and preferably, the aluminum plastic film is used for the shell.
Compared with the prior art, the invention has the beneficial effects that: the invention relates to a preparation method of a self-supporting negative electrode material, which is characterized in that MAX phase materials with high porosity and high specific surface are compounded with high Prussian analogues with excellent electrochemical performance to prepare the electrode material with high conductivity, high reversible specific capacity, difficult lithium precipitation and self-supporting property, the electrode material can be directly used as a negative electrode sheet without a current collector, the electrode material can be normally used as a power-on half electrode after being cut, the addition of a conductive agent, a binder and the like can be omitted, the loading capacity can reach one hundred percent, and meanwhile, the electrode material has certain plasticity in the use process, and the application scene is wider and novel.
Drawings
FIG. 1 is a side SEM image of a self-supporting material of the invention.
Fig. 2 is an SEM image of MXene obtained by exfoliation according to the present invention.
Fig. 3 is a schematic view of the preparation process of the self-supporting anode material of the invention.
FIG. 4 is Ti of the present invention 2 CTx @ MOx composite self-supporting flexible electrode button type lithium ion half-cell cycle curve diagram.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and the accompanying drawings, but the present invention is not limited thereto.
Example 1
A method for preparing a self-supporting anode material, comprising the following steps, as shown in fig. 3:
step S1, mixing hydrochloric acid and lithium fluoride, and adding MAX phase material Ti 2 Performing AlC reaction, adjusting the pH value, performing ultrasonic stirring, centrifuging to obtain MXene dispersion, cooling and storing, wherein the SEM image of MXene is shown in FIG. 2;
step S2, adding Prussian blue analogue Ni into MXene dispersion liquid 2 [Ni(CN) 4 ]Mixing and stirring the mixture and a dispersant sodium dodecyl sulfate, standing, filtering, freezing and drying to obtain a precursor;
and step S3, heating, calcining and oxidizing the precursor to obtain the self-supporting anode material, as shown in FIG. 1.
In step S1, the concentration of hydrochloric acid is 9mol/L, the volume is 10ml, the mass of lithium fluoride is 0.8g, and the mass of MAX phase material is 0.5 g.
Wherein, in the step S1, the reaction time is 24 hours, the pH value is 5, the ultrasonic stirring time is 1 hour, the centrifugation time is 5 minutes, and the centrifugation rotating speed is 3500 rpm/min.
Wherein, theMXene Dispersion and Prussian blue analog Ni in step S2 2 [Ni(CN) 4 ]And the dispersant sodium dodecyl sulfate accounts for 8:3:1.5 in parts by weight.
Among them, Prussian blue analogue Ni 2 [Ni(CN) 4 ]From the transition metal salt NiCl 2 And an organic ligand K 4 [Ni(CN) 4 ]Mixing and reacting according to the molar ratio of 2: 1.
Wherein the heating and calcining temperature in the step S3 is 400 ℃, and the calcining time is 4 hours.
Wherein, the aperture of the suction filtration in the step S2 is 50 μm, and the freeze drying time is 12 hours.
Preparing a negative plate: and cutting the self-supporting negative electrode material prepared by the method to obtain a negative electrode plate.
Preparing a positive plate:
lithium cobaltate, conductive agent superconducting carbon (Super-P) and binder polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 97: 1.5: 1.5, uniformly mixing to prepare lithium ion battery anode slurry with certain viscosity, coating the slurry on a current collector aluminum foil, drying at 85 ℃, and then carrying out cold pressing; then trimming, cutting into pieces, slitting, drying for 4 hours at 110 ℃ under the vacuum condition after slitting, and welding the tabs to prepare the lithium ion battery positive plate.
Preparing an electrolyte:
mixing lithium hexafluorophosphate (LiPF) 6 ) Dissolving the mixture in a mixed solvent composed of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and Ethyl Methyl Carbonate (EMC) (the mass ratio of the three is 1: 2: 1) to obtain the electrolyte with the concentration of 1 mol/L.
Preparing a lithium ion battery:
winding the positive plate, the prepared diaphragm and the negative plate into a battery cell, wherein the oily diaphragm is positioned between the positive plate and the negative plate, the positive electrode is led out by aluminum tab spot welding, and the negative electrode is led out by nickel tab spot welding; and then placing the battery core in an aluminum-plastic packaging bag, injecting the electrolyte, and carrying out processes such as packaging, formation, capacity and the like to prepare the lithium ion battery.
Example 2
The difference from example 1 is that: in the step S1, the concentration of the hydrochloric acid is 5mol/L, the volume is 25ml, the mass of the lithium fluoride is 12g, and the mass of the MAX phase material is 4 g.
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
The difference from example 1 is that: in the step S1, the concentration of the hydrochloric acid is 7mol/L, the volume of the hydrochloric acid is 21ml, the mass of the lithium fluoride is 10g, and the mass of the MAX phase material is 3 g.
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
The difference from example 1 is that: in the step S1, the concentration of the hydrochloric acid is 10mol/L, the volume is 6ml, the mass of the lithium fluoride is 13g, and the mass of the MAX phase material is 2 g.
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
The difference from example 1 is that: in the step S1, the concentration of the hydrochloric acid is 9mol/L, the volume is 10ml, the mass of the lithium fluoride is 1.5g, and the mass of the MAX phase material is 0.2 g.
The rest is the same as embodiment 1, and the description is omitted here.
Example 6
The difference from example 1 is that: in the step S1, the concentration of hydrochloric acid is 9mol/L, the volume is 10ml, the mass of lithium fluoride is 1.5g, and the mass of MAX phase material is 5 g.
The rest is the same as embodiment 1, and the description is omitted here.
Example 7
The difference from example 1 is that: the weight parts of the MXene dispersion liquid, the Prussian analogue and the organic ligand in the step S2 are 8:5: 1.
The rest is the same as embodiment 1, and the description is omitted here.
Example 8
The difference from example 1 is that: the weight parts of the MXene dispersion liquid, the Prussian analogue and the dispersing agent in the step S2 are 8:6: 1.
The rest is the same as embodiment 1, and the description is omitted here.
Example 9
The difference from example 1 is that: the weight parts of the MXene dispersion liquid, the Prussian analogue and the dispersing agent in the step S2 are 6:3: 1.
The rest is the same as embodiment 1, and the description is omitted here.
Example 10
The difference from example 1 is that: the weight parts of the MXene dispersion liquid, the Prussian analogue and the dispersing agent in the step S2 are 4:3: 1.
The rest is the same as embodiment 1, and the description is omitted here.
Example 11
The difference from example 1 is that: the weight parts of the MXene dispersion liquid, the Prussian analogue and the dispersing agent in the step S2 are 7:5: 1.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 1
Graphite, conductive agent superconducting carbon (Super-P), thickening agent carboxymethyl cellulose sodium (CMC) and binder Styrene Butadiene Rubber (SBR) are mixed according to a mass ratio of 96: 2.0: 1.0: 1.0, preparing slurry, coating the slurry on a current collector copper foil, drying at 85 ℃, cutting edges, cutting pieces, dividing strips, drying for 4 hours at 110 ℃ under a vacuum condition after dividing the strips, and welding lugs to prepare the lithium ion battery negative plate.
And (3) performance testing: the negative electrode materials, negative electrode sheets, and secondary batteries prepared in examples 1 to 11 and comparative example 1 were subjected to test performance, and the test results are recorded in table 1.
Cycle capacity retention rate test: charging the lithium ion secondary battery to 4.25V at a constant current of 1C at 25 ℃, then charging to 0.05C at a constant voltage of 4.25V, standing for 5min, and then discharging to 2.8V at a constant current of 1C, wherein the process is a charge-discharge cycle process, and the discharge capacity at this time is the discharge capacity of the first cycle. The lithium ion secondary battery was subjected to 500-cycle charge/discharge tests in accordance with the above-described method, and the discharge capacity per one cycle was recorded. The cycle capacity retention (%) is the discharge capacity at 500 th cycle/discharge capacity at first cycle × 100%.
TABLE 1
| Item | Capacity retention (%) | Item | Capacity retention (%) |
| Example 1 | 89 | Example 2 | 86 |
| Example 3 | 87 | Example 4 | 86 |
| Example 5 | 85 | Example 6 | 87 |
| Example 7 | 84 | Example 8 | 85 |
| Example 9 | 85 | Example 10 | 86 |
| Example 11 | 85 | Comparative example 1 | 72 |
As can be seen from table 1, the self-supporting negative electrode material, the negative electrode sheet and the secondary battery prepared according to the present invention have better capacity retention rate, up to 89%, compared to comparative example 1. As shown in FIG. 4, Ti prepared by the present invention 2 When the CTx @ MOx self-supporting negative electrode material is applied to a composite self-supporting flexible electrode film and is subjected to button lithium ion half-cell cycle performance test, the specific gram capacity of 900mAh/g is still maintained after 500 charge-discharge cycles.
From comparison of examples 1 to 7, when the concentration of hydrochloric acid in the step S1 is set to be 9mol/L, the volume is 10ml, the mass of lithium fluoride is 0.8g, and the mass of the MAX phase material is 0.5g, the prepared self-supporting anode material has better capacity retention rate.
From comparison of examples 1 and 8-11, when the weight parts of the MXene dispersion liquid, the Prussian analogue and the dispersing agent in the S2 are set to be 8:3:1.5, the prepared self-supporting anode material has better capacity retention rate.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious modifications, substitutions or alterations based on the present invention will fall within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. The preparation method of the self-supporting negative electrode material is characterized by comprising the following steps of:
step S1, mixing hydrochloric acid and lithium fluoride, adding MAX phase materials for reaction, adjusting the pH value, ultrasonically stirring, centrifuging to obtain MXene dispersion liquid, cooling and storing;
step S2, adding Prussian blue analogue and dispersant into MXene dispersion liquid, mixing and stirring, standing, performing suction filtration, and performing freeze drying to obtain a precursor;
and step S3, heating, calcining and oxidizing the precursor to obtain the self-supporting negative electrode material.
2. The method for preparing a self-supporting negative electrode material of claim 1, wherein the hydrochloric acid concentration in step S1 is 5-10 mol/L, the volume is 5-25 ml, the mass of the lithium fluoride is 0.2-15 g, and the mass of the MAX phase material is 0.1-5 g.
3. The preparation method of the self-supporting negative electrode material as claimed in claim 1 or 2, wherein the reaction time in the step S1 is 20-30 hours, the pH value is 5-7, the ultrasonic stirring time is 0.5-3 hours, the centrifugation time is 1-10 minutes, and the centrifugation rotation speed is 3000-5000 rpm/min.
4. The method for preparing the self-supporting anode material of claim 1 or 2, wherein the weight parts of the MXene dispersion liquid, the Prussian blue analogue and the dispersing agent in the step S2 are 4-10: 2-6: 1-2.
5. The preparation method of the self-supporting anode material of claim 4, wherein the pore diameter of the suction filtration in the step S2 is 30-50 μm, and the freeze drying time is 10-20 hours.
6. The method for preparing the self-supporting anode material of claim 1, wherein the heating and calcining in the step S3 are performed at 350-600 ℃ for 3-6 hours.
7. A self-supporting material, characterized by being obtained by the method for preparing a self-supporting anode material according to any one of claims 1 to 6.
8. The self-supporting material of claim 7, wherein the thickness of the self-supporting material is 0.01 to 2 mm.
9. A negative electrode sheet, characterized by being the self-supporting material according to claim 7 or 8.
10. A secondary battery comprising the negative electrode sheet according to claim 9.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017076739A (en) * | 2015-10-16 | 2017-04-20 | 国立大学法人 東京大学 | Method for manufacturing electrode material for electrochemical capacitor including layer compound |
| CN110783536A (en) * | 2019-08-19 | 2020-02-11 | 浙江工业大学 | Prussian blue analogue/MXene composite electrode material and in-situ preparation method and application thereof |
| CN114388760A (en) * | 2022-01-14 | 2022-04-22 | 北京化工大学 | Metal oxide nanosheet material, preparation method thereof and lithium ion battery |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017076739A (en) * | 2015-10-16 | 2017-04-20 | 国立大学法人 東京大学 | Method for manufacturing electrode material for electrochemical capacitor including layer compound |
| CN110783536A (en) * | 2019-08-19 | 2020-02-11 | 浙江工业大学 | Prussian blue analogue/MXene composite electrode material and in-situ preparation method and application thereof |
| CN114388760A (en) * | 2022-01-14 | 2022-04-22 | 北京化工大学 | Metal oxide nanosheet material, preparation method thereof and lithium ion battery |
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