CN104409722A - Method for improving performance of lithium manganate cathode material - Google Patents

Method for improving performance of lithium manganate cathode material Download PDF

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Publication number
CN104409722A
CN104409722A CN201410781009.0A CN201410781009A CN104409722A CN 104409722 A CN104409722 A CN 104409722A CN 201410781009 A CN201410781009 A CN 201410781009A CN 104409722 A CN104409722 A CN 104409722A
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lithium
cathode material
manganate cathode
limn2o4
lithium manganate
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CN104409722B (en
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蔡振勇
袁荣忠
李旭
蒋湘康
谭欣欣
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BASF Shanshan Battery Materials Co Ltd
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HUNAN SHANSHAN NEW ENERGY Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00Batteries for particular applications
    • H01M2220/20Batteries in motive systems, e.g. vehicle, ship, plane
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

A method for improving the performance of a lithium manganate cathode material comprises the following steps: (1), washing lithium manganate with a granularity D50 being equal to or smaller than 35 [mu]m by distilled water to remove impurities, and then, dewatering and drying to obtain an impurity-removed lithium manganate product; (2), adding the impurity-removed lithium manganate product into an anionic compound, forging at the constant temperature of 400-600 DEG C for 2-8h after uniformly mixing, then continuously raising the temperature to 700-1000 DEG C, forging at the constant temperature for 7-20h, cooling to a room temperature, and grinding to the granularity D50 being equal to or smaller than 35 [mu]m to obtain the lithium manganate cathode material. According to the invention, the first discharge capacity specific capacity of the lithium manganate cathode material prepared by the method can reach 125mAh/g, and the discharge capacity retention rate of the lithium manganate cathode material being cycled for 50 times at the high temperature of 55 DEG C reaches 95% above. The adoption of the secondary forging of the lithium manganate product in the method can improve the material capacity, enhance the structural stability and improve the material performance. The method adopting simple technology and mild conditions is suitable for massive industrial production.

Description

A kind of method improving manganate cathode material for lithium performance
Technical field
The present invention relates to a kind of method improving manganate cathode material for lithium performance, be specifically related to a kind of aftertreatment LiMn2O4 product to improve the method for manganate cathode material for lithium performance.
Background technology
At present, due to the development of electronic industry technology, electronic product is gradually to miniaturization, and mobile portable phone, camera, notebook computer etc. require power supply miniaturization, high-energy, high power, proposes higher requirement to material.Manganate cathode material for lithium has that low, the easy synthesis of cost, operating voltage are high, environmentally safe and have the advantages such as higher capacity, is one of the most potential lithium ion anode material.But the capacity attenuation of LiMn2O4 is fast, and structural behaviour is unstable, and particularly under the condition of high temperature, cycle performance is very poor, hinders the production of manganate cathode material for lithium scale.
CN102336441B discloses a kind of method that lithium cell anode material lithium manganate prepared by mangano-manganic oxide, after adopting mangano-manganic oxide to mix with lithium salts, pre-burning, double sintering, its discharge capacity is 117.4mAh/g, but this preparation method adopts commercially available mangano-manganic oxide, and purity is lower, introduce impurity in feed stage, effective removal of impurities do not carried out on material after preparation and then affect the performance of material; CN102306767B discloses a kind of preparation method of lithium ion power battery cathode material spinel lithium manganate, by after the manganese dioxide of electrolysis or mangano-manganic oxide, lithium source, metal oxides mixed sintering, its discharge capacity is between 102 ~ 107mAh/g, but the oxygen defect that the method still can not effectively control to cause in sintering process by mixing the elements such as Al, Mg, causes material capacity to decay fast.
Summary of the invention
Technical problem to be solved by this invention is, a kind of cycle performance that can significantly improve manganate cathode material for lithium is provided, particularly under the high temperature conditions, Stability Analysis of Structures, capacity attenuation is slow, and material impedance reduces, and lithium ion is more easily deviate from and embedding, impurity content is low, not easily causes the method for the raising manganate cathode material for lithium performance of oxygen defect during sintering.
The technical solution adopted for the present invention to solve the technical problems is as follows: a kind of method improving manganate cathode material for lithium performance, comprises the following steps:
(1) by the LiMn2O4 distilled water washing impurity-removing of granularity D50≤35 μm, then dehydrate, obtain removal of impurities LiMn2O4 product;
(2) step (1) gained removal of impurities LiMn2O4 product is added the anionic compound being equivalent to its quality 0.05 ~ 3 %, after mixing at 400 ~ 600 DEG C of temperature calcining at constant temperature 2 ~ 8h, then continue to be warmed up to 700 ~ 1000 DEG C of calcining at constant temperature 7 ~ 20h, be cooled to room temperature, be ground to granularity D50≤35 μm, obtain manganate cathode material for lithium.
In step (2), adopt secondary clacining that the part oxygen of LiMn2O4 product surface can be made to be substituted, reduce manganese in LiMn2O4 and dissolve, slow down capacity attenuation.
Further, in step (1), the preparation method of described LiMn2O4 is: lithium source, manganese source and metal oxide are mixed according to elemental lithium, manganese element and metallic element mol ratio 1:1.85 ~ 1.95:0 ~ 0.09, add ethanol furnishing pulpous state, constant temperature pre-burning 5 ~ 10h at 400 ~ 600 DEG C, then continues to be warming up to 800 ~ 1000 DEG C of calcining at constant temperature 15 ~ 24h, is cooled to room temperature, be ground to granularity D50≤35 μm.Obtained LiMn2O4 is lithium manganate having spinel structure, and wherein, a small amount of metal ion that adulterates partly can replace the Mn in LiMn2O4 crystal 3+, to improve the cycle performance of material; Adopt secondary clacining to be conducive to LiMn2O4 crystal structure to be formed.
In the inventive method, LiMn2O4 is except can preparing according to the method described above, can also adopt commercially available lithium manganate having spinel structure.
Further, in step (1), described washing impurity-removing refers to LiMn2O4 washing to sodium ion and sulfate ion total content < 300ppm, other impurity content < 100ppm.Reduce impurity and can improve the stability that LiMn2O4 has structure, reduce the change of structure in charge and discharge process.
Further, in step (2), described anionic compound is one or more in ammonium fluoride, ammonium chloride or ammonium iodide.Add the surface texture that anion can optimize LiMn2O4 product, reduce the damage that electrolyte causes lithium manganate material surface, improve material property further.
Further, in the preparation method of LiMn2O4, described lithium source is one or more in lithium carbonate, lithium hydroxide or lithium acetate; Described manganese source is chemical manganese bioxide or electrolytic manganese dioxide; Described metal oxide is one or more in aluminium oxide, nickel oxide, lanthana or zirconia.
Further, in the preparation method of LiMn2O4, described in add ethanol amount be lithium source, manganese source and metal oxide mixture quality 1 ~ 10%.
Research shows, affect LiMn2O4 product cycle performance and capacity because have external and inherent two factors, external factor is particle uniformity and component uniformity etc.; Internal factor is determined by the intrinsic characteristic of material: the dissolving of (1) Mn: in LiMn2O4, the dissolving of Mn causes lattice defect to make crystal structure disordering, the embedding of lithium ion/deintercalation passage is hindered, affect lithium ion diffusion wherein, cause LiMn2O4 capacity in cyclic process to decline.Under hot conditions, Mn dissolves one of reason is that disproportionated reaction: 2Mn occurs Mn 3+→ Mn 2++ Mn 4+, two of reason is dissolved in acid condition, and under high temperature high potential, electrolyte oxidation Decomposition can produce HF, makes LiMn2O4 be in sour environment, dissolves; (2) Jahn-Teller effect: Jahn-Teller effect causes the irreversible transformation of structure to be the one of the main reasons, particularly Mn of LiMn2O4 cycle performance difference 3+the existence of ion is the essential inducement that this effect occurs, and after LiMn2O4 electric discharge, crystal structure distortion, destroys three-dimensional tunnel structure, and Lithium-ion embeding difficulty, causes capacitance loss.
The inventive method adopts distilled water to wash the LiMn2O4 product prepared, and reduce product impurity content to the impact of properties of product, secondary clacining process not only can make the oxygen on lithium manganate particle surface be substituted, and makes the stable enhancing of product structure.
Compared with prior art, the present invention has the following advantages: (1) the present invention can process lithium manganate having spinel structure product, according to the manganate cathode material for lithium obtained by the inventive method first discharge capacity specific capacity can reach 125mAh/g, compared with the first discharge specific capacity height about 5 ~ 10mAh/g of prior art; Under the hot conditions of 55 DEG C, after 50 circulations, discharge capacitance can reach more than 95%, comparatively prior art high temperature cyclic performance height about 3 ~ 5%, and high temperature cyclic performance is excellent; (2) the inventive method takes secondary clacining LiMn2O4 product, modifies lithium manganate particle surface, and part oxonium ion is substituted, and strengthens the stability of structure, improves the capacity of material, improves the performance of material; (3) XRD of the manganate cathode material for lithium obtained according to the inventive method is known, there is not other the assorted peak except main component characteristic peak in manganate cathode material for lithium, namely impurity phase is not had, show that the optimization of anionic surface does not change the structure of crystal, manganate cathode material for lithium still has spinel cubic crystalline structure; (4) the inventive method technique is simple, mild condition, and proper scale chemical industryization is produced.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram (XRD) of the embodiment of the present invention 1 gained manganate cathode material for lithium;
Fig. 2 is the electron scanning micrograph (SEM) of the embodiment of the present invention 1 gained manganate cathode material for lithium;
Fig. 3 is the embodiment of the present invention 1 gained manganate cathode material for lithium 2C charge/discharge capacity conservation rate variation diagram 55 DEG C time.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the invention will be further described.
embodiment 1
the preparation method of LiMn2O4:
5 mol lithium carbonates and 19 mol electrolytic manganese dioxides are mixed, adds the ethanol furnishing pulpous state being equivalent to mixture quality 5%, be placed in constant temperature pre-burning 8h at Muffle furnace 500 DEG C, then continue to be warming up to 850 DEG C of calcining at constant temperature 20h, be cooled to room temperature, being ground to granularity D50 is 22 μm.
improve the method for manganate cathode material for lithium performance:
(1) be the LiMn2O4 distilled water washing impurity-removing of 22 μm by 1000g granularity D50 be 250ppm to sodium ion and sulfate ion total content, other impurity content is 90ppm, then dehydrates, and obtains removal of impurities LiMn2O4 product;
(2) step (1) gained 1000g removal of impurities LiMn2O4 product is added the mixture of 5g ammonium fluoride and 5g ammonium chloride, after mixing at 530 DEG C of temperature calcining at constant temperature 7h, then continue to be warmed up to 750 DEG C of calcining at constant temperature 18h, be cooled to room temperature, be ground to granularity D50≤22 μm, obtain manganate cathode material for lithium.
From the XRD diffraction pattern of Fig. 1 manganate cathode material for lithium, there is not other the assorted peak except main component characteristic peak in manganate cathode material for lithium, namely do not have impurity phase, show that the optimization of anionic surface does not change the structure of crystal, manganate cathode material for lithium still has spinel cubic crystalline structure; As shown in Figure 2, the present embodiment gained manganate cathode material for lithium surface is comparatively smooth, and size particles is even, and particle diameter is below 22 μm.
battery preparation and test:
By the 93:3:4 ratio mixing in mass ratio of manganate cathode material for lithium, acetylene black and polyvinylidene fluoride, be that solvent is by mixture furnishing pasty state with 1-METHYLPYRROLIDONE, then be coated in uniformly in current collector aluminum foil, roll extrusion after dry, make positive plate, negative pole is disc-shaped lithium metal, and diameter is 12mm; Barrier film is microporous polypropylene membrane (Celgard-2300), and diameter is 14mm; 1.0MLiPF 6ethylene carbonate and diethyl carbonate using mol ratio 3:7 mixing as electrolyte, electrolyte moisture is less than 30ppm; Test battery adopts 2032 type button cells.After tested, discharge capacity specific capacity is 124.5mAh/g first, under the hot conditions of 55 DEG C, through 50 times circulation after, discharge capacitance at 95%(see Fig. 3).
embodiment 2
the preparation method of LiMn2O4:
5 mol lithium hydroxides, 5mol lithium acetate, 19 mol chemical manganese bioxides and 0.4 mol lanthana are mixed, add the ethanol furnishing pulpous state being equivalent to mixture quality 8%, be placed in constant temperature pre-burning 6h at Muffle furnace 450 DEG C, then continue to be warming up to 900 DEG C of calcining at constant temperature 16 h, be cooled to room temperature, being ground to granularity D50 is 8 μm.
improve the method for manganate cathode material for lithium performance:
(1) be the LiMn2O4 distilled water washing impurity-removing of 8 μm by 1000g granularity D50 be 200ppm to sodium ion and sulfate ion total content, other impurity content is 80ppm, then dehydrates, and obtains removal of impurities LiMn2O4 product;
(2) step (1) gained 1000 g removal of impurities LiMn2O4 product is added 0.8 g ammonium fluoride, after mixing at 500 DEG C of temperature calcining at constant temperature 4h, then continue to be warmed up to 950 DEG C of calcining at constant temperature 10h, be cooled to room temperature, be ground to granularity D50≤8 μm, obtain manganate cathode material for lithium.
battery preparation and test:
By the 93:3:4 ratio mixing in mass ratio of manganate cathode material for lithium, acetylene black and polyvinylidene fluoride, be that solvent is by mixture furnishing pasty state with 1-METHYLPYRROLIDONE, then be coated in uniformly in current collector aluminum foil, roll extrusion after dry, make positive plate, negative pole is disc-shaped lithium metal, and diameter is 12mm; Barrier film is microporous polypropylene membrane (Celgard-2300), and diameter is 14mm; 1.0MLiPF 6ethylene carbonate and diethyl carbonate using mol ratio 3:7 mixing as electrolyte, electrolyte moisture is less than 30ppm; Test battery adopts 2032 type button cells.After tested, discharge capacity specific capacity is 125mAh/g first, and under the hot conditions of 55 DEG C, after 50 circulations, discharge capacitance is 96%.
embodiment 3
the preparation method of LiMn2O4:
10mol lithium acetate, 18.8mol electrolytic manganese dioxide, 0.2mol zirconia and 0.2mol nickel oxide are mixed, add the ethanol furnishing pulpous state being equivalent to mixture quality 3%, be placed in constant temperature pre-burning 8h at Muffle furnace 550 DEG C, then continue to be warming up to 950 DEG C of calcining at constant temperature 22h, be cooled to room temperature, being ground to granularity D50 is 30 μm.
improve the method for manganate cathode material for lithium performance:
(1) be the LiMn2O4 distilled water washing impurity-removing of 30 μm by 1000g granularity D50 be 200ppm to sodium ion and sulfate ion total content, other impurity content is 90ppm, then dehydrates, and obtains removal of impurities LiMn2O4 product;
(2) step (1) gained 1000g removal of impurities LiMn2O4 product is added 28g ammonium chloride, after mixing at 550 DEG C of temperature calcining at constant temperature 5h, then continue to be warmed up to 800 DEG C of calcining at constant temperature 8h, be cooled to room temperature, be ground to granularity D50≤30 μm, obtain manganate cathode material for lithium.
battery preparation and test:
By the 93:3:4 ratio mixing in mass ratio of manganate cathode material for lithium, acetylene black and polyvinylidene fluoride, be that solvent is by mixture furnishing pasty state with 1-METHYLPYRROLIDONE, then be coated in uniformly in current collector aluminum foil, roll extrusion after dry, make positive plate, negative pole is disc-shaped lithium metal, and diameter is 12mm; Barrier film is microporous polypropylene membrane (Celgard-2300), and diameter is 14mm; 1.0MLiPF 6ethylene carbonate and diethyl carbonate using mol ratio 3:7 mixing as electrolyte, electrolyte moisture is less than 30ppm; Test battery adopts 2032 type button cells.After tested, discharge capacity specific capacity is 124.5mAh/g first, and under the hot conditions of 55 DEG C, after 50 circulations, discharge capacitance is 95.5%.
embodiment 4
adopt commercially available lithium manganate having spinel structure:
Be 15 μm by the granularity D50 that is ground to of commercially available lithium manganate having spinel structure positive electrode.
improve the method for manganate cathode material for lithium performance:
(1) be the LiMn2O4 distilled water washing impurity-removing of 15 μm by 1000g granularity D50 be 260ppm to sodium ion and sulfate ion total content, other impurity content is 98ppm, then dehydrates, and obtains removal of impurities LiMn2O4 product;
(2) step (1) gained 1000g removal of impurities LiMn2O4 product is added 15g ammonium fluoride, after mixing at 450 DEG C of temperature calcining at constant temperature 6h, then continue to be warmed up to 850 DEG C of calcining at constant temperature 12h, be cooled to room temperature, be ground to granularity D50≤15 μm, obtain manganate cathode material for lithium.
battery preparation and test:
By the 93:3:4 ratio mixing in mass ratio of manganate cathode material for lithium, acetylene black and polyvinylidene fluoride, be that solvent is by mixture furnishing pasty state with 1-METHYLPYRROLIDONE, then be coated in uniformly in current collector aluminum foil, roll extrusion after dry, make positive plate, negative pole is disc-shaped lithium metal, and diameter is 12mm; Barrier film is microporous polypropylene membrane (Celgard-2300), and diameter is 14mm; 1.0MLiPF 6ethylene carbonate and diethyl carbonate using mol ratio 3:7 mixing as electrolyte, electrolyte moisture is less than 30ppm; Test battery adopts 2032 type button cells.After tested, discharge capacity specific capacity is 124mAh/g first, and under the hot conditions of 55 DEG C, after 50 circulations, discharge capacitance is 96%.

Claims (6)

1. improve a method for manganate cathode material for lithium performance, it is characterized in that: comprise the following steps:
(1) by the LiMn2O4 distilled water washing impurity-removing of granularity D50≤35 μm, then dehydrate, obtain removal of impurities LiMn2O4 product;
(2) step (1) gained removal of impurities LiMn2O4 product is added the anionic compound being equivalent to its quality 0.05 ~ 3 %, after mixing at 400 ~ 600 DEG C of temperature calcining at constant temperature 2 ~ 8h, then continue to be warmed up to 700 ~ 1000 DEG C of calcining at constant temperature 7 ~ 20h, be cooled to room temperature, be ground to granularity D50≤35 μm, obtain manganate cathode material for lithium.
2. improve the method for manganate cathode material for lithium performance according to claim 1, it is characterized in that: in step (1), the preparation method of described LiMn2O4 is: lithium source, manganese source and metal oxide are mixed according to elemental lithium, manganese element and metallic element mol ratio 1:1.85 ~ 1.95:0 ~ 0.09, add ethanol furnishing pulpous state, constant temperature pre-burning 5 ~ 10h at 400 ~ 600 DEG C, then continue to be warming up to 800 ~ 1000 DEG C of calcining at constant temperature 15 ~ 24h, be cooled to room temperature, be ground to granularity D50≤35 μm.
3. according to claim 1 or 2, improve the method for manganate cathode material for lithium performance, it is characterized in that: in step (1), described washing impurity-removing refers to LiMn2O4 washing to sodium ion and sulfate ion total content < 300ppm, other impurity content < 100ppm.
4. according to claim 1 or 2, improve the method for manganate cathode material for lithium performance, it is characterized in that: in step (2), described anionic compound is one or more in ammonium fluoride, ammonium chloride or ammonium iodide.
5. improve the method for manganate cathode material for lithium performance according to claim 2, it is characterized in that: described lithium source is one or more in lithium carbonate, lithium hydroxide or lithium acetate; Described manganese source is chemical manganese bioxide or electrolytic manganese dioxide; Described metal oxide is one or more in aluminium oxide, nickel oxide, lanthana or zirconia.
6. improve the method for manganate cathode material for lithium performance according to claim 2, it is characterized in that: described in add ethanol amount be lithium source, manganese source and metal oxide mixture quality 1 ~ 10%.
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CN109534405A (en) * 2018-11-09 2019-03-29 江西智锂科技有限公司 The preparation method of high temperature capacity spinel lithium manganate
CN109742316A (en) * 2018-11-27 2019-05-10 湖北大学 A kind of water system sodium-ion battery electrode and the preparation method and application thereof
KR102038422B1 (en) * 2018-12-19 2019-10-30 한국세라믹기술원 Surface treatment method of lithium transition metal oxide
KR102038421B1 (en) * 2018-12-19 2019-11-26 한국세라믹기술원 Purity degree increase method of electrode active material for lithium ion battery

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CN103022502A (en) * 2012-12-19 2013-04-03 天津巴莫科技股份有限公司 Compounding and coating method of anode material for lithium ion cell
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Publication number Priority date Publication date Assignee Title
CN109534405A (en) * 2018-11-09 2019-03-29 江西智锂科技有限公司 The preparation method of high temperature capacity spinel lithium manganate
CN109742316A (en) * 2018-11-27 2019-05-10 湖北大学 A kind of water system sodium-ion battery electrode and the preparation method and application thereof
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KR102038421B1 (en) * 2018-12-19 2019-11-26 한국세라믹기술원 Purity degree increase method of electrode active material for lithium ion battery

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