CN109867308A - A kind of K2Fe3(SO4)3(OH)2Compound and its preparation and application - Google Patents
A kind of K2Fe3(SO4)3(OH)2Compound and its preparation and application Download PDFInfo
- Publication number
- CN109867308A CN109867308A CN201711257488.6A CN201711257488A CN109867308A CN 109867308 A CN109867308 A CN 109867308A CN 201711257488 A CN201711257488 A CN 201711257488A CN 109867308 A CN109867308 A CN 109867308A
- Authority
- CN
- China
- Prior art keywords
- compound
- containing compound
- ion battery
- sodium ion
- rate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
Abstract
本发明涉及K2Fe3(SO4)3(OH)2化合物及其制备和应用，采用水热法可制备K2Fe3(SO4)3(OH)2化合物和K2Fe3(SO4)3(OH)2/C钠离子电池正极材料；具有较好的钠离子电池充放电性能，循环稳定性良好,工作电压合适，可用作钠离子电池正极材料。
The present invention relates to K 2 Fe 3 (SO 4 ) 3 (OH) 2 compound and its preparation and application. K 2 Fe 3 (SO 4 ) 3 (OH) 2 compound and K 2 Fe 3 (SO 4 ) 2 compound and K 2 Fe 3 (SO 4 ) can be prepared by hydrothermal method 4 ) 3 (OH) 2 /C cathode material for sodium ion battery; it has good charge and discharge performance of sodium ion battery, good cycle stability, suitable working voltage, and can be used as cathode material for sodium ion battery.
Description
技术领域technical field
本发明涉及化学式为K2Fe3(SO4)3(OH)2的化合物、钠离子电池正极材料、这种材料的制备方法以及利用该材料制作钠离子电池。The invention relates to a compound with the chemical formula of K 2 Fe 3 (SO 4 ) 3 (OH) 2 , a positive electrode material for a sodium ion battery, a preparation method of the material, and a sodium ion battery made of the material.
背景技术Background technique
随着能源问题的日益严峻，不可再生资源的日益匮乏，以及人们对环保重要性认识的不断增强，社会对新能源的需求日益增强，而储能在能源体系中发挥越来越重要的作用。之前，作为新能源中重要储能器件的锂离子电池吸引了众多研究资源，但是考虑到锂在地球上的储量较少及其较高的价格，最近对储量更加丰富、更加廉价的K离子电池的研究重新得到了研究者的重视。With the increasingly severe energy problem, the increasing scarcity of non-renewable resources, and the increasing awareness of the importance of environmental protection, the society's demand for new energy is increasing, and energy storage is playing an increasingly important role in the energy system. Previously, lithium-ion batteries, which are important energy storage devices in new energy sources, attracted many research resources. However, considering the relatively small reserves of lithium on earth and its high price, more and more abundant reserves and cheaper K-ion batteries have recently been developed. The research has regained the attention of researchers.
目前应用于钠离子电池的正极材料主要有K3Fe2(PO4)3、KFePO4F、K3Fe2(PO4)2F3和KTiFeO3、KCoO3和KMnO3等。然而，这些材料仍然存在很多问题：比容量和工作电压较低，循环稳定性差及制备困难等，这严重限制了这些材料的实际应用。相比于磷酸盐、硼酸盐和硅酸盐，硫酸盐由于较低的摩尔质量而具有更高的比容量和比能量。硫酸盐具有更窄的带隙和更高的电子电导率。另外，SO4基团也具有诱导效应，可以提高正极材料的工作电压。而目前关于硫酸盐钠离子电池正极材料的研究还很少，值得深入研究。The cathode materials currently used in sodium-ion batteries mainly include K 3 Fe 2 (PO 4 ) 3 , KFePO 4 F, K 3 Fe 2 (PO 4 ) 2 F 3 , KTiFeO 3 , KCoO 3 and KMnO 3 , etc. However, these materials still have many problems: low specific capacity and operating voltage, poor cycling stability and difficult preparation, etc., which severely limit the practical application of these materials. Compared to phosphates, borates and silicates, sulfates have higher specific capacity and specific energy due to their lower molar mass. Sulfates have narrower band gaps and higher electronic conductivity. In addition, the SO4 group also has an inductive effect, which can improve the working voltage of the cathode material. At present, there are few studies on cathode materials for sodium sulfate ion batteries, which are worthy of further study.
发明内容SUMMARY OF THE INVENTION
本发明目的在于提供一种K2Fe3(SO4)3(OH)2化合物及制备方法；The present invention aims to provide a K 2 Fe 3 (SO 4 ) 3 (OH) 2 compound and a preparation method;
本发明另一目的在于提供一种K2Fe3(SO4)3(OH)2/C钠离子电池正极材料Another object of the present invention is to provide a positive electrode material for K 2 Fe 3 (SO 4 ) 3 (OH) 2 /C sodium ion battery
本发明再一目的在于提供一种K2Fe3(SO4)3(OH)2/C钠离子电池正极材料的制备方法；Another object of the present invention is to provide a method for preparing a positive electrode material for K 2 Fe 3 (SO 4 ) 3 (OH) 2 /C sodium ion battery;
本发明的技术方案如下：The technical scheme of the present invention is as follows:
本发明提供的K2Fe3(SO4)3(OH)2化合物。The K 2 Fe 3 (SO 4 ) 3 (OH) 2 compound provided by the present invention.
本发明提供的K2Fe3(SO4)3(OH)2化合物的制备方法，其制备步骤如下：将含K化合物、含Fe化合物和含S化合物按摩尔比K：Fe：S＝2:3:3的比例混合均匀后，进行化学合成反应，制得K2Fe3(SO4)3(OH)2的化合物；The preparation method of the K 2 Fe 3 (SO 4 ) 3 (OH) 2 compound provided by the present invention, the preparation steps are as follows: the K-containing compound, the Fe-containing compound and the S-containing compound are molar ratio K:Fe:S=2: After the ratio of 3:3 is evenly mixed, a chemical synthesis reaction is carried out to obtain a compound of K 2 Fe 3 (SO 4 ) 3 (OH) 2 ;
所述含K化合物为K的氧化物、K的碳酸盐、R的硝酸盐或K的草酸盐；The K-containing compound is K oxide, K carbonate, R nitrate or K oxalate;
所述含Fe化合物为Fe的氧化物、Fe的硫酸盐和Fe的草酸盐；The Fe-containing compound is Fe oxide, Fe sulfate and Fe oxalate;
所述含S化合物为H2SO4、(NH4)2SO4或FeSO4。The S-containing compound is H 2 SO 4 , (NH 4 ) 2 SO 4 or FeSO 4 .
所述K2Fe3(SO4)3(OH)2化合物作为钠离子电池正极活性材料使用，钠离子电池正极材料为K2Fe3(SO4)3(OH)2/C材料，C质量含量为5-50％。The K 2 Fe 3 (SO 4 ) 3 (OH) 2 compound is used as the positive electrode active material of the sodium ion battery, and the positive electrode material of the sodium ion battery is K 2 Fe 3 (SO 4 ) 3 (OH) 2 /C material, and the mass of C The content is 5-50%.
本发明提供的KFE2SO5/C钠离子电池正极材料的制备方法，采用水热法制备K2Fe3(SO4)3(OH)2/C钠离子电池正极材料，其步骤如下：The preparation method of the KFE 2 SO 5 /C sodium ion battery positive electrode material provided by the present invention adopts the hydrothermal method to prepare the K 2 Fe 3 (SO 4 ) 3 (OH) 2 /C sodium ion battery positive electrode material, and the steps are as follows:
1)配料：将含K化合物、含Fe化合物和含S化合物按K:Fe:S:草酸为(1-3):3:(1-3)的摩尔比加入去离子水中搅拌至形成溶液，加入K2Fe3(SO4)3(OH)2质量5％-50％的导电碳Super P,乙炔黑，可乐丽，科琴黑，碳纳米管、石墨烯等)继续搅拌至均匀悬浊液；1) Ingredients: K-containing compound, Fe-containing compound and S-containing compound are added into deionized water at a molar ratio of K:Fe:S:oxalic acid (1-3):3:(1-3) and stirred until a solution is formed, Add K 2 Fe 3 (SO 4 ) 3 (OH) 2 mass 5%-50% conductive carbon Super P, acetylene black, Kuraray, Ketjen black, carbon nanotubes, graphene, etc.) and continue to stir until uniform suspension liquid;
2)将悬浊液移至100ml的带聚四氟乙烯内衬的反应釜中；2) The suspension is moved to the 100ml reactor with Teflon lining;
3)控制各项参数进行材料合成：将盛有上述配料的反应釜置于鼓风烘箱中中；以1-5℃的速率升至150-250℃；保温10-40小时；待反应充分后，以1-50℃/h的速率降至室温，得到K2Fe3(SO4)3(OH)2/C材料；3) Controlling various parameters to synthesize materials: place the reactor containing the above ingredients in a blast oven; raise the temperature to 150-250°C at a rate of 1-5°C; keep the temperature for 10-40 hours; , at a rate of 1-50°C/h to room temperature to obtain K 2 Fe 3 (SO 4 ) 3 (OH) 2 /C material;
所述含K化合物为K的氧化物、K的碳酸盐、K的硫酸盐、K的硝酸盐或K的草酸盐中的一种或二种以上；The K-containing compound is one or more of K oxide, K carbonate, K sulfate, K nitrate or K oxalate;
所述含Fe化合物为Fe的氧化物、Fe的硫酸盐和Fe的草酸盐中的一种或二种以上；The Fe-containing compound is one or more of Fe oxide, Fe sulfate and Fe oxalate;
所述含S化合物为H3SO3、(NH4)2SO4和FeSO4中的一种或二种以上。The S-containing compound is one or more of H 3 SO 3 , (NH 4 ) 2 SO 4 and FeSO 4 .
以下是典型的可得到K2Fe3(SO4)3(OH)2化合物的化学反应：The following are typical chemical reactions that can yield K 2 Fe 3 (SO 4 ) 3 (OH) 2 compounds:
2KOH+3FeSO4＝K2Fe3(SO4)3(OH)2 2KOH+3FeSO 4 =K 2 Fe 3 (SO 4 ) 3 (OH) 2
本发明的优点在于：所获正极材料具有较高的比容量和工作电压，较好的循环稳定性。K2Fe3(SO4)3(OH)2/C钠离子电池正极材料具有较高的比容量达到125mAh/g；其工作电压在2-4.2V之间，100个循环后比容量仍能保持95％以上。The advantages of the invention are that the obtained positive electrode material has higher specific capacity and working voltage, and better cycle stability. K 2 Fe 3 (SO 4 ) 3 (OH) 2 /C sodium ion battery cathode material has a high specific capacity of 125mAh/g; its operating voltage is between 2-4.2V, and the specific capacity can still be maintained after 100 cycles Stay above 95%.
附图说明Description of drawings
图1是本发明K2Fe3(SO4)3(OH)2/C钠离子电池正极材料的SEM图片。FIG. 1 is a SEM picture of the positive electrode material of K 2 Fe 3 (SO 4 ) 3 (OH) 2 /C sodium ion battery of the present invention.
图2为本发明K2Fe3(SO4)3(OH)2/C的多晶粉末X射线衍射图谱。Fig. 2 is a polycrystalline powder X-ray diffraction pattern of K 2 Fe 3 (SO 4 ) 3 (OH) 2 /C of the present invention.
图3为本发明K2Fe3(SO4)3(OH)2的晶体结构图。FIG. 3 is a crystal structure diagram of K 2 Fe 3 (SO 4 ) 3 (OH) 2 of the present invention.
图4为本发明K2Fe3(SO4)3(OH)2/C正极材料0.2C倍率、3-4.3V范围充放电曲线。FIG. 4 is a charge-discharge curve of the K 2 Fe 3 (SO 4 ) 3 (OH) 2 /C positive electrode material of the present invention at a rate of 0.2C and a range of 3-4.3V.
图5为本发明K2Fe3(SO4)3(OH)2/C正极材料在0.2C的循环稳定性曲线。FIG. 5 is the cycle stability curve of the K 2 Fe 3 (SO 4 ) 3 (OH) 2 /C cathode material of the present invention at 0.2C.
具体实施方式Detailed ways
实施例1K2Fe3(SO4)3(OH)2化合物的水热制备Example 1 Hydrothermal Preparation of K 2 Fe 3 (SO 4 ) 3 (OH) 2 Compounds
将0.02mol的KOH溶解于装有50ml去离子水的烧杯中，然后加入0.01mol的FeSO4，在70-80℃的恒温水浴中搅拌至呈绿色溶液，然后加入0.02mol的K2SO4继续搅拌形成绿色溶液。将该溶液置于带有聚四氟乙烯内衬的反应釜中，将反应釜放入鼓风烘箱中。以1-10℃/min的升温速度将炉子升至200℃，保温24小时，最后以1-10℃/min的速度降至室温。将反应产物过滤清洗即得到K2Fe3(SO4)3(OH)2化合物。Dissolve 0.02mol of KOH in a beaker filled with 50ml of deionized water, then add 0.01mol of FeSO4 , stir in a constant temperature water bath at 70-80°C until a green solution, then add 0.02mol of K2SO4 to continue Stir to form a green solution. The solution was placed in a Teflon lined autoclave and the autoclave was placed in a forced air oven. The furnace was raised to 200°C at a heating rate of 1-10°C/min, held for 24 hours, and finally lowered to room temperature at a rate of 1-10°C/min. The reaction product was filtered and washed to obtain K 2 Fe 3 (SO 4 ) 3 (OH) 2 compound.
将实施例1所得复合材料，按照活性物质、导电炭黑、粘结剂二者的质量比为8:1:1溶于适量N-甲基吡咯烷酮中混合均匀，用湿膜制备器涂布成厚度为0.15mm的电极膜，真空烘干后用切片机切成直径为12mm的电极片，称重并计算活性物质的质量。同时以Na片作为正极，以Celgard 2500作为隔膜，1mol/L的NaPF6的EC+DMC(体积比为1:1)的溶液为电解液，在充满氩气的手套箱中装成纽扣电池。然后将装配的电池进行电化学测试，分别在2-4.3V恒流条件下测试。测试结果如图4和5所示，可以看到K2Fe3(SO4)3(OH)2具有较高的放电比容量，达到125mAh/g，且具有良好的倍率性能和循环性能，100个循环容量保持80％以上。The composite material obtained in Example 1 was dissolved in an appropriate amount of N-methylpyrrolidone according to the mass ratio of the active material, conductive carbon black, and binder to be 8:1:1, and mixed evenly, and coated with a wet film preparer to form a composite material. The electrode film with a thickness of 0.15mm was vacuum dried and cut into electrode sheets with a diameter of 12mm with a microtome, weighed and the mass of the active material was calculated. At the same time, the Na sheet was used as the positive electrode, Celgard 2500 was used as the separator, and the EC+DMC (volume ratio of 1:1) solution of 1 mol/L NaPF 6 was used as the electrolyte, and a button battery was installed in an argon-filled glove box. The assembled cells were then electrochemically tested under 2-4.3V constant current conditions, respectively. The test results are shown in Figures 4 and 5. It can be seen that K 2 Fe 3 (SO 4 ) 3 (OH) 2 has a high discharge specific capacity, reaching 125mAh/g, and has good rate performance and cycle performance, 100 The cycle capacity remains above 80%.
对比例1：采用Na0.4MnO2作为正极活性材料应用于钠离子电池中，电池其他条件均同实施例1和2。测试结果显示其比容量只有80mAhg-1，同时其容量在50个循环后就衰减到50mAhg-1。另外，其在5C倍率下充放电容量只剩40mAhg-1。Comparative Example 1: Na 0.4 MnO 2 was used as the positive electrode active material in a sodium-ion battery, and other conditions of the battery were the same as those of Examples 1 and 2. The test results show that its specific capacity is only 80mAhg -1 , and its capacity decays to 50mAhg -1 after 50 cycles. In addition, its charge-discharge capacity at 5C rate is only 40mAhg-1.
对比例2：采用Na3V2(PO4)3作为正极活性材料应用于钠离子电池中，电池其他条件均同实施例1和2。测试结果显示，其容量为105mAhg-1，但是100个循环容量只剩70mAhg-1。在10C倍率下容量保持在60mAhg-1。Comparative Example 2: Na 3 V 2 (PO 4 ) 3 was used as a positive electrode active material in a sodium-ion battery, and other battery conditions were the same as those of Examples 1 and 2. The test results show that its capacity is 105mAhg -1 , but only 70mAhg -1 remains after 100 cycles. The capacity remains at 60mAhg -1 at 10C rate.
通过对比可见，本发明具有较好的钠离子电池充放电性能，循环稳定性和倍率性能良好。It can be seen from the comparison that the present invention has better charge-discharge performance of the sodium ion battery, and has good cycle stability and rate performance.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711257488.6A CN109867308A (en) | 2017-12-04 | 2017-12-04 | A kind of K2Fe3(SO4)3(OH)2Compound and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711257488.6A CN109867308A (en) | 2017-12-04 | 2017-12-04 | A kind of K2Fe3(SO4)3(OH)2Compound and its preparation and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109867308A true CN109867308A (en) | 2019-06-11 |
Family
ID=66914412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711257488.6A Pending CN109867308A (en) | 2017-12-04 | 2017-12-04 | A kind of K2Fe3(SO4)3(OH)2Compound and its preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109867308A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103078111A (en) * | 2011-10-26 | 2013-05-01 | 江苏海四达电源股份有限公司 | Preparation method of monoclinic phase FeSO4·H2O and triclinic phase NaFe1-xMxSO4F (M=Co, Ni) |
| CN104364946A (en) * | 2012-06-12 | 2015-02-18 | 丰田自动车株式会社 | Positive electrode material for sodium batteries and method for producing same |
| CN105206831A (en) * | 2015-08-05 | 2015-12-30 | 北京工业大学 | A preparation method for Na3V2O2x(PO4)2F3-2x microspheres used as positive electrode material for sodium ion batteries |
| CN105271158A (en) * | 2015-09-16 | 2016-01-27 | 湘潭大学 | A kind of preparation method of shuttle-shaped single-layer sheet NaTi2(PO4)3 electrode material |
| CN105762355A (en) * | 2014-12-15 | 2016-07-13 | 中国科学院过程工程研究所 | Vanadium sodium fluorophosphorate, and preparation method and application thereof |
| CN106784718A (en) * | 2016-12-30 | 2017-05-31 | 东莞市佳乾新材料科技有限公司 | A kind of preparation method of high connductivity sodium-ion battery positive material |
| CN106848236A (en) * | 2017-02-20 | 2017-06-13 | 中南大学 | A kind of ferrous sulfate sodium/grapheme composite positive electrode material for sodium-ion battery and preparation method thereof |
| CN106920942A (en) * | 2017-04-01 | 2017-07-04 | 哈尔滨师范大学 | Energy storage electrode material with various polyanion groups and preparation method thereof |
-
2017
- 2017-12-04 CN CN201711257488.6A patent/CN109867308A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103078111A (en) * | 2011-10-26 | 2013-05-01 | 江苏海四达电源股份有限公司 | Preparation method of monoclinic phase FeSO4·H2O and triclinic phase NaFe1-xMxSO4F (M=Co, Ni) |
| CN104364946A (en) * | 2012-06-12 | 2015-02-18 | 丰田自动车株式会社 | Positive electrode material for sodium batteries and method for producing same |
| CN105762355A (en) * | 2014-12-15 | 2016-07-13 | 中国科学院过程工程研究所 | Vanadium sodium fluorophosphorate, and preparation method and application thereof |
| CN105206831A (en) * | 2015-08-05 | 2015-12-30 | 北京工业大学 | A preparation method for Na3V2O2x(PO4)2F3-2x microspheres used as positive electrode material for sodium ion batteries |
| CN105271158A (en) * | 2015-09-16 | 2016-01-27 | 湘潭大学 | A kind of preparation method of shuttle-shaped single-layer sheet NaTi2(PO4)3 electrode material |
| CN106784718A (en) * | 2016-12-30 | 2017-05-31 | 东莞市佳乾新材料科技有限公司 | A kind of preparation method of high connductivity sodium-ion battery positive material |
| CN106848236A (en) * | 2017-02-20 | 2017-06-13 | 中南大学 | A kind of ferrous sulfate sodium/grapheme composite positive electrode material for sodium-ion battery and preparation method thereof |
| CN106920942A (en) * | 2017-04-01 | 2017-07-04 | 哈尔滨师范大学 | Energy storage electrode material with various polyanion groups and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| FUXIANG WANG ET AL.: "K2Fe3(SO4)3(OH)2(H2O)2: A new high-performance hydroxysulfate cathode material for alkali metal ion batteries", 《JOURNAL OF POWER SOURCES》 * |
| KIYOSHI NOMURA ET AL.: "Mossbauer study of giant hard magnetic K2Fe3(OH)2(SO4)3(H2O)2", 《HYERFINE INTERACTIONS》 * |
| WANGWANG XU ET AL.: "Direct growth of an economic green energy storage material: a monocrystalline jarosite-KFe3(SO4)2(OH)6-nanoplates@rGO hybrid as a superior lithium-ion battery cathode", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 吴其胜等: "《新能源材料》", 30 June 2017 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103441241B (en) | A kind of preparation method and application of prussian blue complex/carbon composite material | |
| CN112018349B (en) | A kind of CoTe2/MXene composite material and preparation method thereof | |
| CN105206809B (en) | C3N 4-carbon-coated lithium iron phosphate composite cathode material and preparation method thereof | |
| CN105355890B (en) | The preparation method and application of negative electrode of lithium ion battery zinc sulphide graphene composite material | |
| CN102208641A (en) | One-step synthesis of hollow sphere structure Fe3O4/C lithium-ion battery anode material | |
| CN102208614B (en) | Method for preparing lithium ion battery cathode material coated iron sesquioxide | |
| CN105576223B (en) | A kind of tin oxide base negative electrode material and preparation method thereof with high reversible capacity | |
| CN103594693B (en) | A kind of titanium dioxide/niobium titanium oxide composite material and its preparation and application | |
| CN104393353B (en) | A kind of high magnification and long-life fill room temperature sode cell and preparation method thereof | |
| CN102244255B (en) | Novel cathode material of vanadium oxide nanometer lithium ion battery and preparation method thereof | |
| CN105826524B (en) | A kind of synthetic method of graphene original position forming core LiFePO4 | |
| CN114864945B (en) | Preparation method and application of high-conductivity lithium iron phosphate | |
| CN103531789A (en) | Iron oxide-carbon nanotube ternary composite material and preparation method thereof | |
| CN102339996A (en) | Synthesis and performance of spherical mesoporous anode materials MnO/Mn2O3 for lithium ion battery | |
| CN105047898B (en) | A kind of twin spherical lithium ion secondary battery lithium-rich anode material and preparation method thereof | |
| CN107732203A (en) | A kind of preparation method of nano ceric oxide/graphene/sulphur composite | |
| CN102751503A (en) | Carbon/lithium stannate/graphene composite cathode material of lithium battery and preparation method of material | |
| CN103413940B (en) | A kind of synthetic method of positive material nano lithium manganese phosphate of lithium ion battery | |
| CN104993131B (en) | A kind of lithium ion battery negative material NiS/Ni and preparation method thereof | |
| CN114725375A (en) | One-step solvothermal method for preparing VS2Method for preparing negative electrode material of sodium ion battery | |
| CN103730664A (en) | Positive electrode material of lithium sulfur battery and preparation method and application of material | |
| CN103247801A (en) | Preparation method of high-conductivity lithium iron phosphate cathode material | |
| CN112320792B (en) | Preparation method of negative electrode material for lithium ion battery and product thereof | |
| CN114914437B (en) | A sodium manganese silicate cathode material with high charge transport characteristics based on high-temperature solid-state reaction and its efficient preparation method | |
| CN114242982B (en) | Graphene-coated two-dimensional metal compound electrode material and its preparation method and application |
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: 20190611 |
|
| RJ01 | Rejection of invention patent application after publication |