[go: up one dir, main page]

CN113206253A - Foam copper potassium ion battery material and preparation method thereof - Google Patents

Foam copper potassium ion battery material and preparation method thereof Download PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
ion battery
potassium ion
battery material
copper
foam
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
Application number
CN202110477784.7A
Other languages
Chinese (zh)
Inventor
黄剑锋
何枢薇
李嘉胤
曹丽云
郭玲
王羽偲嘉
王瑜航
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN202110477784.7A priority Critical patent/CN113206253A/en
Publication of CN113206253A publication Critical patent/CN113206253A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

本发明公开了一种泡沫铜钾离子电池材料和制备方法，用于电化学领域作为二次电池材料。包括以下步骤，步骤1，将0.02‑0.08mol/L的硫酸钴溶于无水乙醇与油酸的混合溶液中，搅拌均匀后再加入0.15‑0.45g的硫脲制成反应溶液；步骤2，将预处理后的泡沫铜片放入反应溶液中，将反应溶液升至120℃‑150℃进行溶剂热反应，反应结束后，取出泡沫铜片进行洗涤、干燥后，得到泡沫铜钾离子电池材料。本发明使用泡沫铜作为自支撑体，具有良好的导电性和延展性，作为电池负极材料，泡沫铜基底的三维网状结构将电极材料束缚在其内部，以保持电极的稳定性，提高电池的循环稳定性。在制备电极片的过程中，省去了涂膜的过程，不需要粘结剂和导电剂，减少工艺流程的同时又降低了成本。

Figure 202110477784

The invention discloses a foamed copper-potassium ion battery material and a preparation method, which are used as a secondary battery material in the field of electrochemistry. Including the following steps, step 1, dissolving 0.02-0.08mol/L of cobalt sulfate in a mixed solution of absolute ethanol and oleic acid, stirring evenly, and then adding 0.15-0.45g of thiourea to prepare a reaction solution; step 2, Putting the pretreated foamed copper sheet into the reaction solution, raising the reaction solution to 120°C-150°C for solvothermal reaction, after the reaction is completed, taking out the foamed copper sheet, washing and drying, to obtain the foamed copper-potassium ion battery material . The invention uses foamed copper as a self-supporting body, which has good electrical conductivity and ductility. As a negative electrode material of a battery, the three-dimensional network structure of the foamed copper base binds the electrode material inside it, so as to maintain the stability of the electrode and improve the performance of the battery. Cyclic stability. In the process of preparing the electrode sheet, the process of coating film is omitted, and the binder and the conductive agent are not required, which reduces the process flow and reduces the cost at the same time.

Figure 202110477784

Description

Foam copper potassium ion battery material and preparation method thereof
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.
CN202110477784.7A 2021-04-29 2021-04-29 Foam copper potassium ion battery material and preparation method thereof Pending CN113206253A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110477784.7A CN113206253A (en) 2021-04-29 2021-04-29 Foam copper potassium ion battery material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110477784.7A CN113206253A (en) 2021-04-29 2021-04-29 Foam copper potassium ion battery material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN113206253A true CN113206253A (en) 2021-08-03

Family

ID=77029488

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110477784.7A Pending CN113206253A (en) 2021-04-29 2021-04-29 Foam copper potassium ion battery material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113206253A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118016818A (en) * 2024-04-09 2024-05-10 宁波容百新能源科技股份有限公司 Self-supporting electrode, preparation method thereof and sodium ion battery

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103000906A (en) * 2012-12-13 2013-03-27 天津大学 Preparation method of foamy copper/carbon nanophase composite negative electrode material for lithium ion battery
CN105489899A (en) * 2016-01-26 2016-04-13 长安大学 Lithium ion battery cathode and preparation method thereof
CN106025273A (en) * 2016-07-20 2016-10-12 三峡大学 Preparation method of no-adhesive CuS/Cu sodium ion battery anode
CN107093703A (en) * 2017-04-20 2017-08-25 陕西科技大学 A kind of preparation method of manganese dioxide/foam copper sodium-ion battery self-supporting negative pole
CN107492657A (en) * 2017-07-12 2017-12-19 三峡大学 A kind of preparation method of cobalt sulfide nickel both positive and negative polarity battery and its application on the recyclable battery of alkalescence
CN108039464A (en) * 2017-11-30 2018-05-15 暨南大学 A kind of self-supporting sodium ions to potassium ions battery material and preparation method and application
CN109449394A (en) * 2018-10-19 2019-03-08 陕西科技大学 A kind of flower-shaped (NH4)2V3O8/ foam copper composite material and preparation method and application
CN109888167A (en) * 2019-02-21 2019-06-14 三峡大学 A kind of preparation method of copper-based self-supporting CuO-Cu2O composite array sodium ion anode material
CN110010874A (en) * 2019-04-11 2019-07-12 陕西科技大学 A kind of preparation method of ultra-small spherical cobalt sulfide composite flexible carbon cloth electrode material
CN110534722A (en) * 2019-09-16 2019-12-03 福州大学 A kind of preparation method of novel multi-cavity clad structure bismuth sulfide/cobalt sulfide combination electrode material
CN110711590A (en) * 2019-10-10 2020-01-21 安徽师范大学 A one-dimensional cobalt-sulfur compound/cuprous sulfide composite nanoarray@foamed copper material and its preparation method and application
CN110776017A (en) * 2019-11-26 2020-02-11 陕西科技大学 Cobweb-shaped cobalt sulfide powder and preparation method thereof
CN111081983A (en) * 2019-12-26 2020-04-28 陕西科技大学 A kind of preparation method of Co9S8/carbon felt sodium ion battery self-supporting negative electrode
CN111755695A (en) * 2020-06-30 2020-10-09 陕西科技大学 A kind of wrinkled polyhedral cobalt sulfide electrode material and preparation method thereof
CN112174108A (en) * 2020-09-18 2021-01-05 中国科学技术大学 Preparation method of communicated mesoporous carbon-based composite electrode material

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103000906A (en) * 2012-12-13 2013-03-27 天津大学 Preparation method of foamy copper/carbon nanophase composite negative electrode material for lithium ion battery
CN105489899A (en) * 2016-01-26 2016-04-13 长安大学 Lithium ion battery cathode and preparation method thereof
CN106025273A (en) * 2016-07-20 2016-10-12 三峡大学 Preparation method of no-adhesive CuS/Cu sodium ion battery anode
CN107093703A (en) * 2017-04-20 2017-08-25 陕西科技大学 A kind of preparation method of manganese dioxide/foam copper sodium-ion battery self-supporting negative pole
CN107492657A (en) * 2017-07-12 2017-12-19 三峡大学 A kind of preparation method of cobalt sulfide nickel both positive and negative polarity battery and its application on the recyclable battery of alkalescence
CN108039464A (en) * 2017-11-30 2018-05-15 暨南大学 A kind of self-supporting sodium ions to potassium ions battery material and preparation method and application
CN109449394A (en) * 2018-10-19 2019-03-08 陕西科技大学 A kind of flower-shaped (NH4)2V3O8/ foam copper composite material and preparation method and application
CN109888167A (en) * 2019-02-21 2019-06-14 三峡大学 A kind of preparation method of copper-based self-supporting CuO-Cu2O composite array sodium ion anode material
CN110010874A (en) * 2019-04-11 2019-07-12 陕西科技大学 A kind of preparation method of ultra-small spherical cobalt sulfide composite flexible carbon cloth electrode material
CN110534722A (en) * 2019-09-16 2019-12-03 福州大学 A kind of preparation method of novel multi-cavity clad structure bismuth sulfide/cobalt sulfide combination electrode material
CN110711590A (en) * 2019-10-10 2020-01-21 安徽师范大学 A one-dimensional cobalt-sulfur compound/cuprous sulfide composite nanoarray@foamed copper material and its preparation method and application
CN110776017A (en) * 2019-11-26 2020-02-11 陕西科技大学 Cobweb-shaped cobalt sulfide powder and preparation method thereof
CN111081983A (en) * 2019-12-26 2020-04-28 陕西科技大学 A kind of preparation method of Co9S8/carbon felt sodium ion battery self-supporting negative electrode
CN111755695A (en) * 2020-06-30 2020-10-09 陕西科技大学 A kind of wrinkled polyhedral cobalt sulfide electrode material and preparation method thereof
CN112174108A (en) * 2020-09-18 2021-01-05 中国科学技术大学 Preparation method of communicated mesoporous carbon-based composite electrode material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MINGNA LIAO ET AL.: ""Nanosized CoO Loaded on Copper Foam for High-Performance, Binder-Free Lithium-Ion Batteries"", 《NANOMATERIALS》, vol. 8, no. 4, 22 March 2019 (2019-03-22), pages 1 - 13 *
韩旭等: ""硫化钴锂离子电极材料的制备和应用研究"", 《辽宁石油化工大学学报》, no. 5, 31 October 2020 (2020-10-31), pages 1 - 12 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118016818A (en) * 2024-04-09 2024-05-10 宁波容百新能源科技股份有限公司 Self-supporting electrode, preparation method thereof and sodium ion battery

Similar Documents

Publication Publication Date Title
US11634332B2 (en) Selenium-doped MXene composite nano-material, and preparation method and use thereof
CN110289416A (en) A kind of preparation method of bismuth molybdenum bimetallic sulfide of negative electrode material of sodium ion battery
CN108630919A (en) Carbon-coated silicon/graphene compound and preparation method and application thereof
CN105552366A (en) Preparation method of anode material, namely nitrogen-doped SnS/C composite nanomaterial for lithium battery
CN109286015A (en) A kind of preparation method and application of hollow porous TiO2 nano-cube material
CN111312999A (en) Preparation method of graphene-coated nickel-iron bimetallic sulfide sodium-ion battery negative electrode material
CN111261868A (en) A kind of vanadium pentoxide and its preparation method and application
CN109786711A (en) A kind of preparation method of porous carbon skeleton-coated tin composite electrode material
CN109346717B (en) A kind of self-supporting NaxMnO2 array sodium ion battery cathode material and preparation method thereof
CN112397699B (en) An anion vacancy-rich transition metal chalcogenide/carbon composite material and its preparation method and application
CN117383540A (en) Preparation method of high-magnification modified biomass hard carbon material
CN113206253A (en) Foam copper potassium ion battery material and preparation method thereof
CN112490430A (en) Preparation method of high-performance negative electrode material for lithium/sodium ion battery
CN104638248A (en) Method for preparing graphene/lead compound composite material
CN113012946B (en) Preparation method of phosphorus-doped NiCoB/graphene/fabric electrode material for supercapacitor
CN118791028A (en) A kind of silicon-oxygen composite material coated with aluminum oxide and preparation method thereof
CN102263244B (en) Method for preparing carbon confined-clad Sn/MgO nanowire array for lithium ion battery
CN111899981A (en) Cobalt molybdate nanosheet array electrode material taking three-dimensional graphene foam as substrate, and preparation method and application thereof
CN109755521A (en) A kind of tridimensional network SiO2The preparation method of/C negative electrode material
CN109817954A (en) A kind of preparation method of three-dimensional ordered porous carbon embedded oxide material
CN112038571B (en) Silicon oxide composite negative electrode material and preparation method thereof and lithium ion battery
CN105762350B (en) A kind of high length-diameter ratio nano bar-shape molybdenum trioxide electrode material and preparation method thereof
CN113104898B (en) Application of Li2Fe3(MoO4)4 in Lithium Ion Battery Negative Electrode
CN108892123A (en) A kind of preparation method of porous graphene
CN113140412A (en) Preparation method of electrode material of high-performance super capacitor heterostructure

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: 20210803

RJ01 Rejection of invention patent application after publication