CN113206253A - Foam copper potassium ion battery material and preparation method thereof - Google Patents
Foam copper potassium ion battery material and preparation method thereof Download PDFInfo
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- CN113206253A CN113206253A CN202110477784.7A CN202110477784A CN113206253A CN 113206253 A CN113206253 A CN 113206253A CN 202110477784 A CN202110477784 A CN 202110477784A CN 113206253 A CN113206253 A CN 113206253A
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- 239000006260 foam Substances 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 28
- 229910001414 potassium ion Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- VDNXILQBKLFION-UHFFFAOYSA-N [K].[Cu] Chemical compound [K].[Cu] VDNXILQBKLFION-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 66
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052802 copper Inorganic materials 0.000 claims abstract description 62
- 239000000243 solution Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940044175 cobalt sulfate Drugs 0.000 claims abstract description 13
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims abstract description 13
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 10
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005642 Oleic acid Substances 0.000 claims abstract description 10
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000004729 solvothermal method Methods 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 8
- 239000007773 negative electrode material Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000006258 conductive agent Substances 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- -1 Transition metal sulfides Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005520 electrodynamics Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical compound [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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 invention discloses a foamed copper potassium ion battery material and a preparation method thereof, which are used as secondary battery materials in the field of electrochemistry. The method comprises the following steps of 1, dissolving 0.02-0.08mol/L cobalt sulfate in a mixed solution of absolute ethyl alcohol and oleic acid, uniformly stirring, and then adding 0.15-0.45g thiourea to prepare a reaction solution; and 2, putting the pretreated foam copper sheet into a reaction solution, heating the reaction solution to 120-150 ℃ for solvent thermal reaction, and after the reaction is finished, taking out the foam copper sheet, washing and drying to obtain the foam copper potassium ion battery material. The invention uses the foam copper as a self-supporting body, has good conductivity and ductility, and is used as a battery negative electrode material, and the three-dimensional network structure of the foam copper substrate binds the electrode material in the battery negative electrode material, so that the stability of the electrode is maintained, and the cycle stability of the battery is improved. In the process of preparing the electrode plate, the process of coating is omitted, no binder or conductive agent is needed, the process flow is reduced, and the cost is reduced.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly belongs to a foamed copper potassium ion battery material and a preparation method thereof.
Background
With the progress of science and technology, the performance requirements on materials are higher and higher, and the performance of the traditional single material cannot meet the actual requirements, so that people are prompted to research and prepare composite materials consisting of multiple phases, and the purpose of improving the performance is achieved. Transition metal sulfides tend to have higher theoretical capacity and lower cost. However, the transition metal sulfide has slow electrodynamics and often has large voltage hysteresis, i.e. the charging and discharging platforms are not consistent, which is determined by the reaction mechanism of the transition metal sulfide. The preparation of the cobalt sulfide electrode material is generally carried out by a coating method, and in the process, the capacity contribution of the cobalt sulfide is affected due to the addition of a binder and a conductive agent, and the contact infiltration between an active substance and an electrolyte is hindered, so that the electrochemical reaction cannot be completely reacted. In addition, the coating process is mostly manually completed, certain operation errors exist, and the same experimental steps are difficult to repeat.
In summary, in the preparation process of the battery material in the prior art, substances such as a conductive agent, an adhesive and the like need to be added, and cobalt sulfide has the problems of certain volume expansion, serious pulverization and the like, so that the effective occurrence of a cobalt sulfide conversion reaction is influenced in the charging and discharging process, the phenomena of capacity attenuation, unstable cycling stability, poor rate performance and the like of the cobalt sulfide as a battery electrode material are caused, and the development prospect and application of the cobalt sulfide are seriously influenced.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a foamed copper potassium ion battery material and a preparation method thereof, which are used as secondary battery materials in the field of electrochemistry.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a foam copper potassium ion battery material comprises the following steps,
step 1, dissolving 0.02-0.08mol/L cobalt sulfate in a mixed solution of absolute ethyl alcohol and oleic acid, uniformly stirring, and then adding 0.15-0.45g of thiourea to prepare a reaction solution;
and 2, putting the pretreated foam copper sheet into a reaction solution, heating the reaction solution to 120-150 ℃ for solvent thermal reaction, and after the reaction is finished, taking out the foam copper sheet, washing and drying to obtain the foam copper potassium ion battery material.
Preferably, in step 1, the stirring is magnetic stirring, and the stirring speed is 600-.
Preferably, in step 1, the volume ratio of the oleic acid to the absolute ethyl alcohol is 1: (4-6).
Preferably, in the step 2, the foam copper sheet is completely soaked in acetone and hydrochloric acid solution in sequence for ultrasonic treatment to obtain the pretreated foam copper sheet.
Further, in the step 2, the ultrasonic reaction time of the foam copper sheet in acetone and hydrochloric acid is not less than 30 min.
Further, in the step 2, the concentration of the hydrochloric acid is 2-3 mol/L.
Preferably, in the step 2, the solvothermal reaction time is 8-10 h.
Preferably, in the step 2, the foam copper sheet is washed and alternately cleaned by deionized water and absolute ethyl alcohol for not less than 3 times, and is dried in a vacuum drying oven at the constant temperature of 60 ℃ for 5-8 h.
Preferably, in the step 2, the reaction solution and the foam copper sheet are added into a hydrothermal reaction kettle, and the hydrothermal reaction kettle is sealed and then reacts in a homogeneous phase reactor at a rotating speed of 6-10 r/min.
A foamed copper potassium ion battery material is prepared based on any one of the preparation methods.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention provides a preparation method of a foamed copper potassium ion battery material, which is used for preparing a cobalt sulfide/foamed copper composite electrode material by a simple one-step solvothermal method, is easy to achieve experimental conditions, is environment-friendly, does not need high-temperature calcination, avoids volume expansion of cobalt sulfide in the calcination process, and enables crystals to be regular and ordered in appearance, small in particle size and uniform in distribution. The invention uses the foam copper as a self-supporting body, has good conductivity and ductility, and is used as a battery negative electrode material, and the three-dimensional network structure of the foam copper substrate binds the electrode material in the battery negative electrode material, so that the stability of the electrode is maintained, and the cycle stability of the battery is improved. Meanwhile, the problem of volume expansion in the charging and discharging process can be relieved. In the process of preparing the electrode plate, the process of coating is omitted, no binder or conductive agent is needed, the process flow is reduced, and the cost is reduced.
Furthermore, the foam copper sheet is pretreated to remove oxides and impurities on the foam copper sheet, so that the impurities on the foam copper sheet are prevented from influencing the preparation process.
The prepared foamy copper potassium ion battery material has the advantages of uniform chemical composition, high purity and uniform appearance, and can show excellent electrochemical performance when being used as a potassium ion battery electrode material.
Drawings
FIG. 1 is an XRD of the product of example 1 of the present invention.
FIG. 2 is a low magnification SEM of the product of example 1 of the present invention.
FIG. 3 is a high power SEM of the product made in example 1 of the present invention.
FIG. 4 is a graph of cycle test performance of the product prepared in example 1 of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1:
1) dissolving cobalt sulfate in a mixed solution of 40mL of absolute ethyl alcohol and 10mL of oleic acid, and performing magnetic stirring at a rotating speed of 600r/min to prepare a clear solution A, wherein the concentration of the cobalt sulfate is 0.02 mol/L;
2) adding 0.15g of thiourea into the solution A, and stirring at the same rotating speed to obtain a uniformly mixed solution B;
3) cutting the self-supporting substrate foam copper with the thickness of 1mm into foam copper sheets with the size of 3 multiplied by 3cm, and sequentially and completely soaking the foam copper sheets in acetone and 2mol/L hydrochloric acid solution for ultrasonic treatment for 30min to obtain pretreated foam copper sheets; the pretreatment is used for removing oxides and impurities on the foam copper and avoiding the impurities on the foam copper sheet from influencing the preparation process.
4) Transferring the solution B into a hydrothermal reaction kettle, simultaneously putting a pretreated foam copper sheet, sealing, and carrying out a solvothermal reaction in a homogeneous reactor reaction instrument. Carrying out solvent thermal reaction for 8h at the rotating speed of 6r/min from room temperature to 120 ℃, alternately cleaning the product for 3 times by using deionized water and absolute ethyl alcohol after the reaction is finished, and drying for 5h at the constant temperature of 60 ℃ in a vacuum drying oven.
The XRD pattern of the product of example 1 of the invention can be seen in FIG. 1, from which it can be seen that the cobalt sulphide product is Co4S3At the same time, part of the simple substances Cu and Cu2And S. This shows that during the reaction, part of the sulfur source reacts with Cu on the foamed copper substrate to generate a small amount of Cu2S, belonging to the normal phenomenon.
From fig. 2, the macroscopic morphology of the product prepared in example 1 of the present invention can be seen, and from the macroscopic morphology, it can be seen that cobalt sulfide uniformly grows on both sides of the copper foam, and the distribution is regular.
From fig. 3, it can be seen that the high power morphology of the product prepared in example 1 of the present invention is shown, and from the figure, it can be seen that the flaky cobalt sulfide is interlaced with each other, and forms a micron spherical structure with a certain porosity. The electrode material is convenient for the insertion and the separation of potassium ions in the charging and discharging process, and shortens the transmission path of the potassium ions, so that the electrode material has faster transmission dynamics, and the electrochemical performance of the electrode is improved.
From fig. 4, it can be seen that the cycle test chart of the product prepared in example 1 of the present invention as the negative electrode material of the potassium ion battery has a capacity of 395.5mAh/g after 100 cycles under a current density of 0.2A/g, and the product has excellent cycle stability and a high capacity in the same cobalt sulfide-based material.
Example 2:
1) dissolving cobalt sulfate in a mixed solution of 43mL of absolute ethyl alcohol and 9mL of oleic acid, and performing magnetic stirring at a rotation speed of 650r/min to prepare a clear solution A, wherein the concentration of the cobalt sulfate is 0.04 mol/L;
2) adding 0.2g of thiourea into the solution A, and stirring at the same rotating speed to obtain a uniformly mixed solution B;
3) cutting the self-supporting substrate foam copper with the thickness of 1mm into foam copper sheets with the size of 3 multiplied by 3cm, and sequentially and completely soaking the foam copper sheets in acetone and 2.2mol/L hydrochloric acid solution for ultrasonic treatment for 40min to obtain pretreated foam copper sheets;
4) transferring the solution B into a hydrothermal reaction kettle, simultaneously placing a pretreated foam copper sheet, sealing, heating from room temperature to 130 ℃ in a homogeneous phase reactor at a rotating speed of 7r/min for solvent thermal reaction for 8.5h, after the reaction is finished, alternately cleaning the product for 3 times by using deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at a constant temperature of 60 ℃ for 6 h.
Example 3:
1) dissolving cobalt sulfate in a mixed solution of 40mL of absolute ethyl alcohol and 8mL of oleic acid, and performing magnetic stirring at the rotating speed of 700r/min to prepare a clear solution A, wherein the concentration of the cobalt sulfate is 0.05 mol/L;
2) adding 0.25g of thiourea into the solution A, and stirring at the same rotating speed to obtain a uniformly mixed solution B;
3) cutting the self-supporting substrate foam copper with the thickness of 1mm into foam copper sheets with the size of 3 multiplied by 3cm, and sequentially and completely soaking the foam copper sheets in acetone and 2.5mol/L hydrochloric acid solution for respectively carrying out ultrasonic treatment for 50min to obtain pretreated foam copper sheets;
4) transferring the solution B into a hydrothermal reaction kettle, simultaneously placing a pretreated foam copper sheet, sealing, carrying out solvent thermal reaction for 9h in a homogeneous phase reactor at the rotating speed of 8r/min from room temperature to 140 ℃, alternately cleaning the product for 3 times by using deionized water and absolute ethyl alcohol after the reaction is finished, and drying for 7h in a vacuum drying oven at the constant temperature of 60 ℃.
Example 4:
1) dissolving cobalt sulfate in a mixed solution of 42mL of absolute ethyl alcohol and 7mL of oleic acid, and performing magnetic stirring at a rotating speed of 750r/min to prepare a clear solution A, wherein the concentration of the cobalt sulfate is 0.06 mol/L;
2) adding 0.3g of thiourea into the solution A, and stirring at the same rotating speed to obtain a uniformly mixed solution B;
3) cutting the self-supporting substrate foam copper with the thickness of 1mm into foam copper sheets with the size of 3 multiplied by 3cm, and sequentially and completely soaking the foam copper sheets in acetone and 2.8mol/L hydrochloric acid solution for ultrasonic treatment for 60min to obtain pretreated foam copper sheets;
4) transferring the solution B into a hydrothermal reaction kettle, simultaneously placing a pretreated foam copper sheet, sealing, heating from room temperature to 145 ℃ in a homogeneous phase reactor at a rotating speed of 9r/min for carrying out solvent thermal reaction for 9.5h, after the reaction is finished, alternately cleaning the product for 3 times by using deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at a constant temperature of 60 ℃ for 7.5 h.
Example 5:
1) dissolving cobalt sulfate in a mixed solution of 36mL of absolute ethyl alcohol and 6mL of oleic acid, and performing magnetic stirring at the rotating speed of 800r/min to prepare a clear solution A, wherein the concentration of the cobalt sulfate is 0.08 mol/L;
2) adding 0.45g of thiourea into the solution A, and stirring at the same rotating speed to obtain a uniformly mixed solution B;
3) cutting the self-supporting substrate foam copper with the thickness of 1mm into foam copper sheets with the size of 3 multiplied by 3cm, and sequentially and completely soaking the foam copper sheets in acetone and 3mol/L hydrochloric acid solution for ultrasonic treatment for 70min to obtain pretreated foam copper sheets;
4) transferring the solution B into a hydrothermal reaction kettle, simultaneously placing a pretreated foam copper sheet, sealing, heating from room temperature to 150 ℃ in a homogeneous phase reactor at a rotating speed of 10r/min for solvent thermal reaction for 10h, after the reaction is finished, alternately cleaning the product for 3 times by using deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at a constant temperature of 60 ℃ for 8 h.
Claims (10)
1. A preparation method of a foam copper potassium ion battery material is characterized by comprising the following steps,
step 1, dissolving 0.02-0.08mol/L cobalt sulfate in a mixed solution of absolute ethyl alcohol and oleic acid, uniformly stirring, and then adding 0.15-0.45g of thiourea to prepare a reaction solution;
and 2, putting the pretreated foam copper sheet into a reaction solution, heating the reaction solution to 120-150 ℃ for solvent thermal reaction, and after the reaction is finished, taking out the foam copper sheet, washing and drying to obtain the foam copper potassium ion battery material.
2. The method for preparing the copper foam potassium ion battery material as claimed in claim 1, wherein in step 1, the stirring is magnetic stirring, and the stirring speed is 600-800 r/min.
3. The method for preparing the copper foam potassium ion battery material as claimed in claim 1, wherein in the step 1, the volume ratio of the oleic acid to the absolute ethyl alcohol is 1: (4-6).
4. The method for preparing the copper foam potassium ion battery material according to claim 1, wherein in the step 2, the copper foam sheet is completely soaked in acetone and hydrochloric acid solution in sequence for ultrasonic treatment to obtain the pretreated copper foam sheet.
5. The method for preparing the copper foam potassium ion battery material as claimed in claim 4, wherein in the step 2, the ultrasonic reaction time of the copper foam sheet in acetone and hydrochloric acid is not less than 30 min.
6. The method for preparing the copper foam potassium ion battery material according to claim 4, wherein in the step 2, the hydrochloric acid concentration is 2-3 mol/L.
7. The method for preparing the copper foam potassium ion battery material as claimed in claim 1, wherein in the step 2, the solvothermal reaction time is 8-10 h.
8. The method for preparing the copper foam potassium ion battery material as claimed in claim 1, wherein in the step 2, the copper foam sheet is washed and alternately cleaned with deionized water and absolute ethyl alcohol for not less than 3 times, and dried in a vacuum drying oven at a constant temperature of 60 ℃ for 5-8 h.
9. The method for preparing the copper foam potassium ion battery material according to claim 1, wherein in the step 2, the reaction solution and the copper foam sheet are added into a hydrothermal reaction kettle, and the hydrothermal reaction kettle is sealed and then reacts in a homogeneous phase reactor at a rotating speed of 6-10 r/min.
10. A copper foam potassium ion battery material, characterized by being prepared based on the preparation method of any one of claims 1 to 9.
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