CN108039464A - A kind of self-supporting sodium ions to potassium ions battery material and preparation method and application - Google Patents
A kind of self-supporting sodium ions to potassium ions battery material and preparation method and application Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
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- H—ELECTRICITY
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
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Abstract
The invention discloses a kind of self-supporting sodium ions to potassium ions battery material and preparation method and application.The self-supporting sodium ions to potassium ions battery material is specially porous sulfur doping graphene aerogel, and the content of its sulphur is 2~10wt%, and structure is the three-dimensional structure that flake graphite alkene is self-assembly of.Graphene oxide water solution first obtains graphene aerogel with freeze-drying after ammonium hydroxide reaction, then reacts with sulphur steam to obtain porous sulfur doping graphene aerogel at high temperature.It will can be used for sodium ions to potassium ions battery cathode in a manner of self-supporting after the porous sulfur doping graphene aerogel compacting.There is the specific capacity of superelevation using the porous sulfur doping graphene aerogel as the sodium ions to potassium ions battery of anode, excellent cycle characteristics, the advantages that good multiplying power, compared to other non-self-supporting negative materials, the self-supporting material can reduce the use of collector, binding agent, more easily realize the raising of sodium ions to potassium ions battery performance.
Description
Technical field
The present invention relates to sodium ions to potassium ions battery correlative technology field, and in particular to a kind of self-supporting sodium ions to potassium ions battery material
Material and preparation method and application.
Background technology
In order to meet the intermittence of the growing energy demand of modern society and energy supply, a large amount of regenerative resources
As wind energy, solar energy, biomass, tide energy and geothermal energy are developed.But since it has intermittence, it is therefore desirable to efficient storage
Energy technology stores it.Lithium ion battery is since it has the advantages that energy density is high, has extended cycle life, in numerous schemes
In become presently the most suitable energy storage technology.But the large-scale application of lithium ion battery is also faced with price limit at the same time
System and resource constraint.For this reason, to become mesh previous important standby for sodium-ion battery and kalium ion battery with more price advantage
Select scheme.Since sodium ion has more excellent price advantage, the research to sodium-ion battery, especially with respect to suitable
Anode material of lithium-ion battery research, be of great significance to current energy storage field.Simultaneously as K/K+Oxidation
Reduction potential is -2.92V vs NHE, less than Na/Na+Oxidation-reduction potential (- 2.71V vs NHE), therefore, with sodium from
In the comparison of sub- battery, kalium ion battery shows the energy density of higher.Since the performance of sodium ions to potassium ions battery is mainly by it
Electrode material determines, therefore finds a kind of high performance sodium ions to potassium ions cell negative electrode material and become that current one is important to grind
Study carefully hot spot.
From Constantine's Nuo Woxiao loves of University of Manchester in 2004 single-layer graphene is separated using Mechanical Method
Since, the concern for a large amount of researchers that its relevant research attracts.Compared to other carbon materials, graphene shows super large
Specific surface area, excellent electrical conductance etc..It helps to improve the electric conductivity of material in porous, electrically conductive network is formed.Used
When kalium ion battery negative material, it has relatively low cubical expansivity during deintercalation is carried out with potassium ion.But
Due to capacity of the graphene in sodium ions to potassium ions battery and its coulombic efficiency is relatively low first, this greatly limits it in potassium
Application in ion battery.There is corresponding report to confirm sulfur doping carbon material in lithium ion battery and sodium ion electricity at present
Chi Zhongke effectively improves its chemical property (Chem.Commun., 48 (2012) 10663；Electrochim.Acta,241
(2017)63).Meanwhile materials application as also having had associated class is in aluminium ion battery (Chinese patent application
CN201410416398.7).But up to the present, it is being used for sodium-ion battery certainly on sulfur doping porous graphene aeroge
Support anode is not reported also accordingly, and the related application in kalium ion battery then more lacks.With other secondary cells
(such as lithium, aluminium ion battery) is compared, and sodium ions to potassium ions is due to the radius with bigger, therefore it is required that sulfur doping carbon material used has
There are the insertion interlamellar spacing and pore passage structure of bigger, and the above-mentioned prior art is not met by the requirement of sodium ions to potassium ions battery.
The content of the invention
The defects of in order to solve the above-mentioned prior art and deficiency, primary and foremost purpose of the invention be to provide a kind of self-supporting sodium/
Kalium ion battery material.
It is a further object of the present invention to provide the preparation method of above-mentioned self-supporting sodium ions to potassium ions battery material.The preparation side
Method is easy and effective, of low cost, and obtained self-supporting sodium ions to potassium ions battery material has coulombic efficiency height, specific capacity first
The characteristics such as height, stable circulation.
Another object of the present invention is to provide above-mentioned self-supporting sodium ions to potassium ions battery material as self-supporting sodium-ion battery
The application of anode and kalium ion battery anode.
The present invention concrete technical scheme be：
A kind of self-supporting sodium ions to potassium ions battery material, sulfur doping is obtained in graphene aerogel, wherein the content of sulphur
For 2~10wt%；Structure is the three-dimensional structure that flake graphite alkene is self-assembly of, and the diameter macropores being made of flake graphite alkene are
2~50 μm, the aperture diameter in graphene layer is 5~20nm.
A kind of preparation method of self-supporting sodium ions to potassium ions battery material, this method include step in detail below：
(1) suitable ammonium hydroxide is added into graphene oxide water solution, it is freeze-dried after stirring evenly, finally
Obtain graphite oxide aerogel；
(2) graphite oxide aerogel and sulphur powder obtained step (1) mixes and carries out heat under inert gas atmosphere
Processing, then cooling obtain porous sulfur doping graphene aerogel, i.e., described self-supporting sodium ions to potassium ions battery material；Wherein oxygen
Graphite alkene aeroge and the mass ratio of sulphur powder are 1：1~5, heat treatment temperature is 400~1000 DEG C, heat treatment time 0.5
~4 it is small when.
In heat treatment process, since sulphur distils, sulphur steam reacts with graphene at high temperature, initially enters carbon
In lattice.Unnecessary sulphur removes in gaseous form.It adulterates sulfur content and is mainly determined by the sulphur powder added.Heat treatment temperature and
Time can influence the degree of carbon graphite.Processing time is long and treatment temperature is excessive, the graphitization of porous sulfur doping graphene
Degree is higher, is unfavorable for the insertion of potassium ion.Processing time is too short and treatment temperature is too low, then due to the reduction of graphene oxide
Not enough, containing a large amount of oxygen groups, it is unfavorable for the storage of potassium ion.
Pass through the sulphur steam in high temperature and graphite oxide alkene reaction, during graphene oxide reduces, sulphur atom meeting
Substitute the carbon in graphene and oxygen position.By optimizing the content of sulphur, the ratio of graphitic carbon can be made to be lower, so optimize potassium from
The reactivity and stability of sulphur and potassium in sub- battery, make material have the insertion interlamellar spacing and more preferably pore passage structure of bigger
(including aperture and potassium ion transfer passages).While interlamellar spacing and pore passage structure is optimized, collapsing for loose structure is also prevented
Collapse, reasonably graphene surface punching, reasonably mix sulphur etc. in graphene surface, be just adaptable to by multiple technological means
Kalium ion battery.The doping content of sulphur needs strictly to be controlled, and also needs to ensure the circulation longevity while embedding capacity is improved
Life.When sulfur content is excessive, the insertion of sodium ions to potassium ions can increase, but since its volumetric expansion aggravates, its cycle life is rapid
Decline, be unfavorable for it and prepare for having macrocyclic kalium ion battery.
Step (1) described graphene oxide can use commercial goods, can also be prepared by changing Hummer methods,
Comprise the following steps that：
(a) graphite powder, sodium nitrate are added to the concentrated sulfuric acid of 98wt%, graphite powder, sodium nitrate, the concentrated sulfuric acid pair in 0 DEG C
The mass ratio answered is 1：1：40；
(b) after step (a) resulting solution being stirred 30 minutes uniformly, it is slowly added to the matter of potassium permanganate, wherein graphite powder
The mass ratio of amount and potassium permanganate is 1：3；
(c) step (b) resulting solution reacted at 35~40 DEG C 2~8 it is small when, original solution body is then diluted at 0 DEG C
Long-pending 4~8 times, add the hydrogen peroxide equivalent to liquor capacity 1~8%, cleaning, so as to obtain graphene oxide water solution.
Preferably, the concentration of step (1) described graphene oxide water solution is 2~10mg/mL.
Preferably, the volume ratio of step (1) ammonium hydroxide and graphene oxide water solution is 0.5~2%.
Preferably, when step (1) mixing time is 1~24 small.
Preferably, step (1) the freeze-drying condition is to be freeze-dried 2~4 days at -40~-80 DEG C.
Application of the above-mentioned self-supporting sodium ions to potassium ions battery material as self-supporting kalium ion battery anode, will be described porous
Sulfur doping graphene aerogel is cut into suitable shape after flattening and size can be used as self-supporting kalium ion battery anode.
Application of the above-mentioned self-supporting sodium ions to potassium ions battery material as self-supporting sodium-ion battery anode, will be described porous
Sulfur doping graphene aerogel is cut into suitable shape after flattening and size can be used as self-supporting sodium-ion battery anode.
Compared with prior art, the invention has the advantages that：
(1) present invention heat treatment after cold do prepares porous sulfur doping graphene aerogel, and first with the side of self-supporting
Formula uses it for sodium ions to potassium ions cell negative electrode material, and compared with conventional electrode materials, this electrode can be effective using self-supporting technique
The use of collector, binding agent is reduced, so as to be easier to improve total specific capacity of the sodium ions to potassium ions battery；
(2) when porous sulfur doping graphene aerogel is used as self-supporting sodium ions to potassium ions battery cathode electrode, there is storehouse first
The advantages that human relations are efficient, specific capacity is high, cycle performance and high rate performance are excellent.Meanwhile preparation method of the present invention is simple, condition temperature
With, it is of low cost, it is easy to accomplish industrial scale application.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of porous sulfur doping graphene aerogel prepared by the embodiment of the present invention 1；
The element sulphur distribution map for the porous sulfur doping graphene aerogel that Fig. 2 right figures are prepared for the embodiment of the present invention 1, left figure
For the scanning electron microscope (SEM) photograph of corresponding region；
Fig. 3 is the transmission electron microscope picture of porous sulfur doping graphene aerogel prepared by the embodiment of the present invention 1；
Fig. 4 is the Raman spectrogram of porous sulfur doping graphene aerogel prepared by the embodiment of the present invention 1；
Fig. 5 be the embodiment of the present invention 1 prepare porous sulfur doping graphene aerogel as self-supporting electrode in potassium ion
Cycle performance figure in battery；
Fig. 6 be the embodiment of the present invention 1 prepare porous sulfur doping graphene aerogel as self-supporting electrode in potassium ion
Front and rear comparison diagram is circulated in battery；
Fig. 7 be the embodiment of the present invention 1 prepare porous sulfur doping graphene aerogel as self-supporting electrode in potassium ion
High rate performance figure in battery；
Fig. 8 be the embodiment of the present invention 1 prepare porous sulfur doping graphene aerogel as self-supporting electrode in potassium ion
Long circulation life figure in battery；
Fig. 9 be the embodiment of the present invention 1 prepare porous sulfur doping graphene aerogel as self-supporting electrode in sodium ion
Cycle performance figure in battery.
Embodiment
With reference to specific embodiment mode, which is further elaborated.It is to be understood that these embodiments are only used
It is used to limit the scope of the invention in illustrating rather than.
Embodiment 1
(1) preparation of graphene oxide
(a) 3g graphite powders and 3g sodium nitrate are added to the 98wt% concentrated sulfuric acids of 120g in 0 DEG C；
(b) after step (a) resulting solution being stirred 30 minutes uniformly, it is slowly added to 9g potassium permanganate.
(c) 5 times of original solution volume are slowly diluted to after reacting 2h at 35 DEG C to step (b) resulting solution, at 0 DEG C,
10mL hydrogen peroxide is added, it is cleaned multiple times with dilute hydrochloric acid, then is cleaned with deionized water, obtained brown solution is
Graphene oxide water solution.
(2) preparation of graphite oxide aerogel
In the graphene oxide water solution of 500mL 2mg/mL add 10mL concentrated ammonia liquors, stirring 24 it is small when after, used
Refrigerator is freezed, then it is freeze-dried, and freeze-drying is set to -50 DEG C, obtains graphite oxide aerogel.
(3) preparation of porous sulfur doping graphene aerogel material
Graphite oxide aerogel is mixed with sulphur powder, wherein the mass ratio of graphite oxide aerogel and sulphur powder is 1：2,
When 600 DEG C of heat treatments 2 are small in a nitrogen atmosphere again, porous sulfur doping graphene aerogel is obtained after cooling.Corresponding scanning electricity
Mirror figure is as shown in Figure 1, the three-dimensional that porous sulfur doping graphene aerogel is made of graphene nanometer sheet as can be observed from Figure
Structure.Element sulphur distribution map is as shown in Fig. 2, element sulphur is uniformly distributed in porous sulfur doping graphene gas as can be observed from Figure
On gel.Transmission electron microscope picture is as shown in figure 3, as can be observed from Figure in prepared porous sulfur doping graphene aerogel
There are substantial amounts of cavernous structure for nanometer sheet.Raman spectrogram from figure as shown in figure 4, can substantially observe the Raman that it is carbon
Peak, wherein after sulfur doping, D peaks and the ratio at G peaks become higher, and show the change that its graphitic carbon tails off, its interfloor distance also occurs,
This all provides extraordinary condition to the storage performance of kalium ion battery.By optimizing the content of sulphur, the ratio of graphitic carbon can be made
Value is lower, and then optimizes the reactivity and stability of sulphur and potassium in kalium ion battery, material is had the embeding layer of bigger
Spacing and more preferably pore passage structure.
Embodiment 2
(1) preparation of graphene oxide
(a) 3g graphite powders and 3g sodium nitrate are added to the 98wt% concentrated sulfuric acids of 120g in 0 DEG C；
(b) after step (a) resulting solution being stirred 30 minutes uniformly, it is slowly added to 9g potassium permanganate.
(c) 5 times of original solution volume are slowly diluted to after reacting 2h at 35 DEG C to step (b) resulting solution, at 0 DEG C,
10mL hydrogen peroxide is added, it is cleaned multiple times with dilute hydrochloric acid, then is cleaned with deionized water, obtained brown solution is
Graphene oxide water solution.
(2) preparation of graphite oxide aerogel
In the graphene oxide water solution of 500mL 10mg/mL add 10mL concentrated ammonia liquors, stirring 24 it is small when after, used
Refrigerator is freezed, then it is freeze-dried, and freeze-drying is set to -50 DEG C, obtains graphite oxide aerogel.
(3) preparation of porous sulfur doping graphene aerogel material
Graphite oxide aerogel is mixed with sulphur powder, wherein the mass ratio of graphite oxide aerogel and sulphur powder is 1：5,
When 1000 DEG C of heat treatments 2 are small in a nitrogen atmosphere again, porous sulfur doping graphene aerogel is obtained after cooling.
Embodiment 3
(1) preparation of graphene oxide
(a) 3g graphite powders and 3g sodium nitrate are added to the 98wt% concentrated sulfuric acids of 120g in 0 DEG C；
(b) after step (a) resulting solution being stirred 30 minutes uniformly, it is slowly added to 9g potassium permanganate.
(c) 5 times of original solution volume are slowly diluted to after reacting 2h at 35 DEG C to step (b) resulting solution, at 0 DEG C,
10mL hydrogen peroxide is added, it is cleaned multiple times with dilute hydrochloric acid, then is cleaned with deionized water, obtained brown solution is
Graphene oxide water solution.
(2) preparation of graphite oxide aerogel
In the graphene oxide water solution of 500mL 5mg/mL add 1mL concentrated ammonia liquors, stirring 1 it is small when after, used ice
Case is freezed, then it is freeze-dried, and freeze-drying is set to -50 DEG C, obtains graphite oxide aerogel.
(3) preparation of porous sulfur doping graphene aerogel material
Graphite oxide aerogel is mixed with sulphur powder, wherein the mass ratio of graphite oxide aerogel and sulphur powder is 1：1,
When 400 DEG C of heat treatments 2 are small in a nitrogen atmosphere again, porous sulfur doping graphene aerogel is obtained after cooling.
Embodiment 4
The circular electric of a diameter of 14mm is tailored into after porous sulfur doping graphene aerogel prepared by embodiment 1 is flattened
Pole.Using metallic potassium as reference electrode and to electrode, by the use of Whatman GF/C as membrane, be respectively less than in water, oxygen content
Button cell is assembled into the argon gas atmosphere glove box of 0.5ppm.The 1M Potassium Hexafluorophosphates of use are dissolved in ethylene carbonate, carbonic acid
The mixed solvent of methyl ethyl ester (1 ︰ 1 of mass ratio).Button cell carries out constant current charge-discharge (0.01- by new prestige cell tester
3V), the chemical property of copper sulfide/graphene composite material is tested.
Fig. 5 is porous sulfur doping graphene aerogel self-supporting anode in above-mentioned potassium ion button cell 100mA/g's
Cycle performance under current density.Reversible specific capacity is up to 439mAh/g to the electrode first, and specific capacity still may be used after 50 circulations
To keep 339mAh/g, capacity retention ratio 77.2%, is demonstrated by good cycle performance.Front and rear electrode will be circulated to carry out pair
Than (Fig. 6) it is observed that the electrode still remains a complete self-supporting electrode.It is it can be seen that porous made from embodiment 1
Sulfur doping graphene aerogel is used as possessing extraordinary storage potassium performance during anode in a manner of self-supporting.
As shown in fig. 7, porous sulfur doping graphene aerogel self-supporting anode is in difference in above-mentioned potassium ion button cell
High rate performance is tested under current density 100mA/g, 250mA/g, 500mA/g, 1000mA/g.It is 1000mA/g in current density
When, the specific capacity of porous sulfur doping graphene aerogel self-supporting anode still reaches 208mAh/g, shows superior multiplying power
Performance.
As shown in figure 8, above-mentioned potassium ion button cell tests the battery long circulating longevity also under high current density 1000mA/g
Life, after the charge and discharge cycles of 1000 times, porous sulfur doping graphene aerogel self-supporting anode, which remains unchanged, keeps the specific volume of stabilization
Amount.
Embodiment 5
Porous sulfur doping graphene aerogel made from embodiment 1 is also used for sodium-ion battery as self-supporting anode material
Material.Sodium-ion battery assembling comprises the following steps that：Graphene aerogel self-supporting electrode is tailored into the circle of a diameter of 14mm
Electrode.Using metallic sodium as reference electrode and to electrode, by the use of Whatman GF/C as membrane, be respectively less than in water, oxygen content
Button cell is assembled into the argon gas atmosphere glove box of 0.5ppm.The 1M sodium hexafluoro phosphates of use are dissolved in ethylene carbonate, carbonic acid
The mixed solvent of methyl ethyl ester (1 ︰ 1 of mass ratio).Button cell carries out constant current charge-discharge (0.01- by new prestige cell tester
3V), its chemical property is tested.
Fig. 9 is porous sulfur doping graphene aerogel self-supporting anode in above-mentioned sodium ion button cell 100mA/g's
Cycle performance under current density.Reversible specific capacity is up to 448mAh/g to the electrode first, and specific capacity still may be used after 50 circulations
To keep 340mAh/g, capacity retention ratio 75.8%.Kalium ion battery by comparing embodiment 4 and the sodium to embodiment 5
For the performance of ion battery it can be found that both chemical properties are more similar, this represents electrode material tool made from embodiment 1
There is very excellent storage sodium/potassium performance.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
- A kind of 1. self-supporting sodium ions to potassium ions battery material, it is characterised in that sulfur doping is obtained in graphene aerogel, its The content of middle sulphur is 2~10wt%；Structure is the three-dimensional structure that flake graphite alkene is self-assembly of, and is made of flake graphite alkene Diameter macropores are 2~50 μm, and the aperture diameter in graphene layer is 5~20nm.
- 2. a kind of preparation method of self-supporting sodium ions to potassium ions battery material, it is characterised in that comprise the following steps：(1) suitable ammonium hydroxide is added into graphene oxide water solution, it is freeze-dried after stirring evenly, is finally obtained Graphite oxide aerogel；(2) graphite oxide aerogel and sulphur powder obtained step (1) is mixed and is heat-treated under inert gas atmosphere, Then cooling obtains porous sulfur doping graphene aerogel, i.e., described self-supporting sodium ions to potassium ions battery material；Wherein graphite oxide Alkene aeroge and the mass ratio of sulphur powder are 1：1~5, heat treatment temperature is 400~1000 DEG C, and heat treatment time is small for 0.5~4 When.
- 3. the preparation method of self-supporting sodium ions to potassium ions battery material according to claim 2, it is characterised in that step (1) The concentration of the graphene oxide water solution is 2~10mg/mL.
- 4. the preparation method of self-supporting sodium ions to potassium ions battery material according to claim 2, it is characterised in that step (1) The volume ratio of the ammonium hydroxide and graphene oxide water solution is 0.5~2%.
- 5. the preparation method of self-supporting sodium ions to potassium ions battery material according to claim 2, it is characterised in that step (1) When the mixing time is 1~24 small.
- 6. the preparation method of self-supporting sodium ions to potassium ions battery material according to claim 2, it is characterised in that step (1) The freeze-drying condition is to be freeze-dried 2~4 days at -40~-80 DEG C.
- 7. the self-supporting sodium ions to potassium ions battery material described in claim 1 is as self-supporting kalium ion battery anode or self-supporting The application of sodium-ion battery anode.
- 8. self-supporting sodium ions to potassium ions battery material according to claim 7 is as self-supporting kalium ion battery anode or certainly Support the application of sodium-ion battery anode, it is characterised in that the specific method of the application is：By the porous sulfur doping graphite Alkene aeroge is cut into suitable shape after flattening and size can be used as self-supporting kalium ion battery anode or self-supporting sodium from Sub- battery cathode.
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Cited By (8)
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| CN109004186A (en) * | 2018-06-15 | 2018-12-14 | 陕西科技大学 | A kind of preparation method of multiple exotic atom doping three-dimensional grapheme |
| CN109786691A (en) * | 2018-12-24 | 2019-05-21 | 肇庆市华师大光电产业研究院 | A kind of kalium ion battery negative electrode material and preparation method thereof |
| CN109860578A (en) * | 2019-03-20 | 2019-06-07 | 暨南大学 | Application of the artificial gold-grapheme material collaboration ethers electrolyte in kalium ion battery |
| CN111106348A (en) * | 2019-12-31 | 2020-05-05 | 上海理工大学 | Sulfur-modulated universal carbon-based negative electrode material for alkali metal ion battery and preparation method thereof |
| CN112117436A (en) * | 2020-09-24 | 2020-12-22 | 北京化工大学 | Novel two-dimensional carbon composite flexible electrode of sodium ion battery and preparation method thereof |
| CN113206253A (en) * | 2021-04-29 | 2021-08-03 | 陕西科技大学 | Foam copper potassium ion battery material and preparation method thereof |
| CN114975972A (en) * | 2022-07-07 | 2022-08-30 | 华南师范大学 | Preparation method of potassium ion battery negative electrode material |
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| CN109004181A (en) * | 2018-06-15 | 2018-12-14 | 陕西科技大学 | A kind of preparation method of nitrogen sulphur codope graphene aerogel self-supporting electrode |
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| CN109786691B (en) * | 2018-12-24 | 2020-10-20 | 肇庆市华师大光电产业研究院 | Potassium ion battery negative electrode material and preparation method thereof |
| CN109860578A (en) * | 2019-03-20 | 2019-06-07 | 暨南大学 | Application of the artificial gold-grapheme material collaboration ethers electrolyte in kalium ion battery |
| CN111106348A (en) * | 2019-12-31 | 2020-05-05 | 上海理工大学 | Sulfur-modulated universal carbon-based negative electrode material for alkali metal ion battery and preparation method thereof |
| CN112117436A (en) * | 2020-09-24 | 2020-12-22 | 北京化工大学 | Novel two-dimensional carbon composite flexible electrode of sodium ion battery and preparation method thereof |
| CN113206253A (en) * | 2021-04-29 | 2021-08-03 | 陕西科技大学 | Foam copper potassium ion battery material and preparation method thereof |
| CN114975972A (en) * | 2022-07-07 | 2022-08-30 | 华南师范大学 | Preparation method of potassium ion battery negative electrode material |
| CN114975972B (en) * | 2022-07-07 | 2024-03-26 | 华南师范大学 | Preparation method of anode material of potassium ion battery |
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