CN104466100A - Lithium-based positive electrode material for sodion secondary battery, preparation method of lithium-based positive electrode material and sodion battery - Google Patents

Lithium-based positive electrode material for sodion secondary battery, preparation method of lithium-based positive electrode material and sodion battery Download PDF

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Publication number
CN104466100A
CN104466100A CN201410765630.8A CN201410765630A CN104466100A CN 104466100 A CN104466100 A CN 104466100A CN 201410765630 A CN201410765630 A CN 201410765630A CN 104466100 A CN104466100 A CN 104466100A
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positive electrode
secondary battery
ion secondary
sodium ion
lithium
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杜菲
魏芷宣
魏英进
王春忠
陈岗
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Jilin University
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Jilin University
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection 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
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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 provides a lithium-based positive electrode material for a sodion secondary battery, and belongs to the field of sodion secondary batteries. The material has the molecular formula of Li(NiCoMn)1/3O2, has a hexagonal layered structure, and the space group is as shown in the specification. The invention also provides a preparation method of the lithium-based positive electrode material of the sodion secondary battery, and the sodion battery prepared from the lithium-based positive electrode material. According to the invention, Li(NiCoMn)1/3O2 firstly acts as the sodion battery positive electrode material, and the sodion battery has relatively good electrochemical performance. The experiment result shows that in the voltage interval of 2.0-4.3V, the initial charge specific capacity of the sodion battery reaches 176.4mAh/g, and the initial discharge specific capacity reaches 157.6mAh/g. The capacity can reach 99.2mAh/g after the battery is charged and discharged for 20 times.

Description

A kind of lithium base sodium ion secondary battery positive electrode, preparation method and sodium-ion battery
Technical field
The present invention relates to sodium ion secondary battery field, be specifically related to a kind of lithium base sodium ion secondary battery positive electrode, preparation method and sodium-ion battery.
Background technology
Along with population in the world increases, economic development, a large amount of consumption of the energy and the pollution of environment, the exploitation of clean sustainable novel energy have become a problem demanding prompt solution.Lithium rechargeable battery is high as a kind of energy density, good cycle, security performance are good, the green energy resource of memory-less effect, has been widely used in the small electrical equipment for gasification such as mobile phone, laptop computer, electric motor car.But although elemental lithium extensively distributes, its reserves in the earth's crust does not enrich, and after lithium battery widespread commercial, the limited increase that result in material cost of the supply of lithium.And in contrast, sodium element is considered to a kind of lower cost materials because of its reserves abundant in the earth's crust, in addition, the reaction mechanism of sodium ion secondary battery system and " rocking chair type " of lithium ion battery react very similar, therefore, sodium-ion battery is regarded as replacing the excellent selection that lithium ion battery becomes the extensive energy storing device of a new generation.
Along with the attention of researcher to sodium ion secondary battery increases day by day, the research and development of novel sodium-ion battery positive material becomes the study hotspot of association area in recent years.Some layered cathode materials are as Na x[Fe 1/2mn 1/2] O 2, NaNi 0.5ti 0.5o 2, Na 1-xni ymn zco 1-y-zo 2and polyanionic positive electrode is as Na 1.5vPO 4.8f 0.7, Na 2(Fe xmn 1-x) P 2o 7, Na 3mnPO 4cO 3deng demonstrating the application prospect attracted people's attention.But the shortcoming that the sodium ion secondary battery ubiquity capacity assembled as positive pole of these materials is on the low side, usually within the scope of 80mAh/g-120mAh/g.At present not by Li (NiCoMn) 1/3o 2as patent or the document of sodium ion secondary battery positive electrode.
Summary of the invention
The object of the invention is to solve sodium ion secondary battery capacity problem on the low side, a kind of lithium base sodium ion secondary battery positive electrode, preparation method and sodium-ion battery are provided.
First the present invention provides a kind of lithium base sodium ion secondary battery positive electrode, and this material molecule formula is Li (NiCoMn) 1/3o 2, have six side's layer structures, space group is
The present invention also provides the preparation method of lithium base sodium ion secondary battery positive electrode, comprising:
Step one: by NiSO 46H 2o, CoSO 47H 2o and MnSO 4h 2o mixes, at N 2under protection, react at 60 ~ 80 DEG C, obtain reaction solution;
Step 2: instilled by alkali lye in the reaction solution of step one, stirring reaction, is precipitated thing emulsion;
Step 3: sediment emulsion acid-base value step 2 obtained is adjusted to neutrality, dries, obtains presoma;
Step 4: the presoma that step 3 is obtained and Li 2cO 3mixing, then places in Muffle furnace and carries out presintering, obtain mix powder;
Step 5: the mix powder compressing tablet that step 4 is obtained, and be placed in Muffle furnace and sinter, obtain lithium base sodium ion secondary battery positive electrode.
Preferably, described step one NiSO 46H 2o, CoSO 47H 2o and MnSO 4h 2the mol ratio of Ni, Co and Mn in O is 1:1:1.
Preferably, the alkali lye of described step 2 is the mixed solution of NaOH and ammoniacal liquor.
Preferably, the temperature of presintering in described step 4 is 400 ~ 500 DEG C, and the time is 4 ~ 6 hours.
Preferably, the sintering temperature of described step 5 is 900 DEG C ~ 950 DEG C, and the time is 12 ~ 24 hours.
The sodium-ion battery that the present invention also provides above-mentioned lithium base sodium ion secondary battery positive electrode to prepare.
Beneficial effect of the present invention
First the present invention provides a kind of lithium base sodium ion secondary battery positive electrode, and this material molecule formula is Li (NiCoMn) 1/3o 2, the present invention is first by Li (NiCoMn) 1/3o 2use as sodium ion secondary battery positive electrode.
The present invention also provides a kind of preparation method of lithium base sodium ion secondary battery positive electrode, and this preparation method can make raw material refinement and Homogeneous phase mixing, and properties of product are good, and this preparation method is energy-conservation, efficient, pollution-free, simple to operate, and suitable batch is produced.
The sodium-ion battery that the present invention mainly provides a kind of above-mentioned lithium base sodium ion secondary battery positive electrode to prepare, this sodium-ion battery is owing to have employed positive electrode of the present invention, and this sodium-ion battery has good chemical property.Experimental result shows: sodium ion secondary battery of the present invention sodium-ion battery initial charge of the present invention specific capacity reaches 176.4mAh/g, and first discharge specific capacity reaches 157.6mAh/g, and battery is after experience 20 discharge and recharges, and capacity can reach 99.2mAh/g.
Accompanying drawing explanation
Fig. 1 is Li (NiCoMn) prepared by the embodiment of the present invention 1 1/3o 2the X ray diffracting spectrum of dusty material.
Fig. 2 is Li (NiCoMn) prepared by the embodiment of the present invention 1 1/3o 2first three charging and discharging curve figure of dusty material.
Fig. 3 is Li (NiCoMn) prepared by the embodiment of the present invention 1 1/3o 2the cycle performance curve chart of dusty material.
Embodiment
First the present invention provides a kind of lithium base sodium ion secondary battery positive electrode, and this material molecule formula is Li (NiCoMn) 1/3o 2, have six side's layer structures, space group is
The present invention also provides the preparation method of lithium base sodium ion secondary battery positive electrode, comprising:
Step one: by NiSO 46H 2o, CoSO 47H 2o and MnSO 4h 2o mixes, at N 2under protection, react at 60 ~ 80 DEG C, obtain reaction solution;
Step 2: instilled by alkali lye in the reaction solution of step one, stirring reaction, is precipitated thing emulsion;
Step 3: sediment emulsion acid-base value step 2 obtained is adjusted to neutrality, dries, obtains presoma;
Step 4: the presoma that step 3 is obtained and Li 2cO 3mixing, then places in Muffle furnace and carries out presintering, obtain mix powder;
Step 5: the mix powder compressing tablet that step 4 is obtained, and be placed in Muffle furnace and sinter, obtain lithium base sodium ion secondary battery positive electrode.
According to the present invention, described in step one with NiSO 46H 2o, CoSO 47H 2o, MnSO 4h 2o is raw material, preferred NiSO 46H 2o, CoSO 47H 2o and MnSO 4h 2the mol ratio of Ni, Co and Mn in O is 1:1:1, takes reactant and puts into four-hole bottle and add deionized water, be stirred to and seal without after particle, pass into N 2protection, is heated to 60 ~ 80 DEG C, obtains reaction solution;
According to the present invention, instilled by alkali lye in above-mentioned reaction solution, stop instillation when solution ph is 12, Keep agitation 12 ~ 24 hours, is precipitated thing emulsion; Described alkali lye is preferably the mixed solution that alkali lye is NaOH and ammoniacal liquor, and described NaOH and the mol ratio of ammoniacal liquor are preferably 1:2.
According to the present invention, sediment emulsion obtained above is preferably rinsed repeatedly with distilled water and is adjusted to neutrality to acid-base value, be precipitated thing oven dry and obtain presoma; Described bake out temperature is preferably 110-130 DEG C, and drying time is 10-24 hour.
According to the present invention, by presoma obtained above and 5% excessive Li 2cO 3mixing, grinding, compressing tablet, carries out presintering in Muffle furnace, naturally cools and obtains mix powder; Owing to there will be the phenomenon of part lithium source volatilization in sintering process, in process of lapping, therefore need the Li adding 5% extra mass 2cO 3; The temperature of presintering is preferably 400 ~ 500 DEG C, and the time is preferably 4 ~ 6 hours.
According to the present invention, by said mixture pressed powder, and be placed in Muffle furnace and sinter, cooling obtains lithium base sodium ion secondary battery positive electrode naturally; Described sintering temperature is preferably 900 DEG C ~ 950 DEG C, and the time is preferably 12 ~ 24 hours.
The sodium-ion battery that the present invention also provides above-mentioned lithium base sodium ion secondary battery positive electrode to prepare.The preparation method of sodium-ion battery of the present invention is the technical method that this area is commonly used, and is not particularly limited, preferably includes: by the Li (NiCoMn) prepared 1/3o 2material, conductive auxiliary agent and binding agent are mixed into slurry according to certain mass ratio, and concrete ratio can regulate as requested, is not particularly limited, the preferred Li of the present invention (NiCoMn) 1/3o 2material, acetylene black and PVDF (Kynoar) are mixed into slurry according to the ratio of mass ratio 7:2:1, afterwards by obtained slurry even application in aluminum substrates, by the electrode slice drying more than 10 hours in vacuum drying oven obtained, compression process is carried out to the electrode slice of drying, then the pole piece of system is cut into size be applicable to thin slice as positive pole, in the glove box being full of argon gas (content of water and oxygen is less than 1PPM) be assembled into experimental cell.The present invention is half-cell to electrode with pure sodium sheet, and the barrier film of battery adopts GLASS MICROFIBER FILTERS GF/C tMbarrier film, electrolyte can adopt various types of liquid electrolyte or solid electrolyte, and the present invention is preferably to be dissolved in the organic electrolyte of PC solvent containing 1mol/L sodium perchlorate.Experimental cell carries out charge and discharge cycles test by by computer-controlled auto charge and discharge instrument.
Below in conjunction with specific embodiment, further detailed description is done to the present invention.The raw material NiSO related in embodiment 46H 2o, MnSO 4h 2o is that Chemical Reagent Co., Ltd., Sinopharm Group produces; CoSO 47H 2o is that Tianjin great Mao chemical reagent factory is produced; Li 2cO 3for Sigma-Aldrich company produces.
Embodiment 1
Take 0.01molNiSO 46H 2o, 0.01molCoSO 47H 2o, 0.01molMnSO 4h 2o puts into four-hole bottle and adds about 200mL deionized water, is stirred to and seals without after particle, pass into N 2protection, is heated to 60 DEG C; Preparation mol ratio is that the NaOH of 1:2, ammoniacal liquor mixed solution are for subsequent use; Buret is inserted four-hole bottle, and by above-mentioned obtained alkali lye by buret to solution slowly titration, in this process, solution is added thermal magnon strong stirring, when solution ph is 12 stop instillation, Keep agitation 12 hours; Repeatedly sediment is rinsed until sediment emulsion acid-base value is in neutral with distilled water; Take out after gained sediment being put into 120 DEG C of oven for drying 12h, obtain presoma; Presoma and 5% excessive Li 2cO 3mixed grinding, compressing tablet, in Muffle furnace, carry out pre-burning the temperature of 400 DEG C, be incubated 4 hours, naturally cool; Gained pressed powder, sinters the temperature of 900 DEG C in Muffle furnace, is incubated 12 hours, naturally cools, obtains sodium ion secondary battery positive electrode.
Fig. 1 is Li (NiCoMn) prepared by the embodiment of the present invention 1 1/3o 2x-ray diffraction (XRD) collection of illustrative plates of dusty material.Specific experiment method is: use the Bruker D8 diffractometer being equipped with copper target X-ray tube to carry out X-ray powder diffraction test to sample.Sample is being produced out an even curface in circular sample groove, and its thickness and width meet the condition of test needs.As can be seen from Figure 1, this material of XRD spectrum display obtained has layer structure, and belong to hexagonal crystal system, space group is xRD is sharply linear, and there is no other diffracted ray and exist, show that material structure is complete, free from admixture exists mutually.
The sodium ion secondary battery positive electrode that embodiment 1 is obtained, acetylene black and PVDF (Kynoar) are mixed into slurry according to the ratio of 7:2:1, even application is in aluminum substrates, after the electrode slice obtained is dried 10 hours in the vacuum drying oven of 120 DEG C, tight at 22MPa pressure, then the pole piece of system is cut into the thin slice that is of a size of 8mm × 8mm as positive pole (active material containing about 1.7mg on each thin slice), being half-cell with pure sodium sheet, (diameter is for about 1cm to electrode, thickness is the disk of about 3mm), with the sodium perchlorate containing 1mol/L for solute, PC is the organic liquid of solvent configuration is electrolyte, in the glove box being full of argon gas (content of water and oxygen is less than 1PPM) be assembled into experimental cell.Fig. 2 is Li (NiCoMn) prepared by the embodiment of the present invention 1 1/3o 2first three charging and discharging curve figure of dusty material.Fig. 3 is Li (NiCoMn) prepared by the embodiment of the present invention 1 1/3o 2the cycle performance curve chart of dusty material, as can be seen from Figures 2 and 3, Li (NiCoMn) prepared by example 1 of the present invention 1/3o 2dusty material is tested under 2.0 ~ 4.3V voltage range as positive electrode, and current density is 100mA/g, and its initial charge specific capacity reaches 176.4mAh/g, and first discharge specific capacity reaches 157.6mAh/g.After experiencing 20 discharge and recharges, battery specific capacity is 99.2mAh/g.
Embodiment 2
Take 0.005molNiSO 46H 2o, 0.005molCoSO 47H 2o, 0.005molMnSO 4h 2o puts into four-hole bottle and adds about 200mL deionized water, is stirred to and seals without after particle, pass into N 2protection, is heated to 70 DEG C; Preparation mol ratio is that the NaOH of 1:2, ammoniacal liquor mixed solution are for subsequent use; Buret is inserted four-hole bottle, and by above-mentioned obtained alkali lye by buret to solution slowly titration, in this process, solution is added thermal magnon strong stirring, when solution ph is 12 stop instillation, Keep agitation 18 hours; Repeatedly sediment is rinsed until sediment emulsion acid-base value is in neutral with distilled water; Take out after gained sediment being put into 120 DEG C of oven for drying 12h, obtain presoma; Presoma and 5% excessive Li 2cO 3mixed grinding, compressing tablet, in Muffle furnace, carry out pre-burning the temperature of 450 DEG C, be incubated 5 hours, naturally cool; Gained pressed powder, sinters the temperature of 950 DEG C in Muffle furnace, is incubated 20 hours, naturally cools, obtains sodium ion secondary battery positive electrode.
Positive electrode embodiment 2 obtained is assembled into experimental cell according to the method for embodiment 1, experimental result shows: to discharge to described battery with the current density of 100mA/g in 2.0 ~ 4.3V voltage range and charge, initial charge specific capacity reaches 192.7mAh/g, specific discharge capacity is 151.7mAh/g, battery is after experience 20 discharge and recharges, and capacity is about 97.9mAh/g.
Embodiment 3
Take 0.02molNiSO 46H 2o, 0.02molCoSO 47H 2o, 0.02molMnSO 4h 2o puts into four-hole bottle and adds about 200mL deionized water, is stirred to and seals without after particle, pass into N 2protection, is heated to 80 DEG C; Preparation mol ratio is that the NaOH of 1:2, ammoniacal liquor mixed solution are for subsequent use; Buret is inserted four-hole bottle, and by above-mentioned obtained alkali lye by buret to solution slowly titration, in this process, solution is added thermal magnon strong stirring, when solution ph is 12 stop instillation, Keep agitation 24 hours; Repeatedly sediment is rinsed until sediment emulsion acid-base value is in neutral with distilled water; Take out after gained sediment being put into 120 DEG C of oven for drying 12h, obtain presoma; Presoma and 5% excessive Li 2cO 3mixed grinding, compressing tablet, in Muffle furnace, carry out pre-burning the temperature of 500 DEG C, be incubated 6 hours, naturally cool; Gained pressed powder, sinters the temperature of 900 DEG C in Muffle furnace, is incubated 24 hours, naturally cools, obtains sodium ion secondary battery positive electrode.
Positive electrode embodiment 3 obtained is assembled into experimental cell according to the method for embodiment 1, experimental result shows: to discharge to described battery with the current density of 100mA/g in 2.0 ~ 4.3V voltage range and charge, initial charge specific capacity reaches about 163.4mAh/g, specific discharge capacity is 143.1mAh/g, battery is after experience 20 discharge and recharges, and capacity is about 105.8mAh/g.

Claims (7)

1. a lithium base sodium ion secondary battery positive electrode, is characterized in that, this material molecule formula is Li (NiCoMn) 1/3o 2, have six side's layer structures, space group is
2. the preparation method of a kind of lithium base sodium ion secondary battery positive electrode according to claim 1, is characterized in that, comprising:
Step one: by NiSO 46H 2o, CoSO 47H 2o and MnSO 4h 2o mixes, at N 2under protection, react at 60 ~ 80 DEG C, obtain reaction solution;
Step 2: instilled by alkali lye in the reaction solution of step one, stirring reaction, is precipitated thing emulsion;
Step 3: sediment emulsion acid-base value step 2 obtained is adjusted to neutrality, dries, obtains presoma;
Step 4: the presoma that step 3 is obtained and Li 2cO 3mixing, then places in Muffle furnace and carries out presintering, obtain mix powder;
Step 5: the mix powder compressing tablet that step 4 is obtained, and be placed in Muffle furnace and sinter, obtain lithium base sodium ion secondary battery positive electrode.
3. the preparation method of a kind of lithium base sodium ion secondary battery positive electrode according to claim 2, is characterized in that, described step one NiSO 46H 2o, CoSO 47H 2o and MnSO 4h 2the mol ratio of Ni, Co and Mn in O is 1:1:1.
4. the preparation method of a kind of lithium base sodium ion secondary battery positive electrode according to claim 2, it is characterized in that, the alkali lye of described step 2 is the mixed solution of NaOH and ammoniacal liquor.
5. the preparation method of a kind of lithium base sodium ion secondary battery positive electrode according to claim 2, it is characterized in that, the temperature of presintering in described step 4 is 400 ~ 500 DEG C, and the time is 4 ~ 6 hours.
6. the preparation method of a kind of lithium base sodium ion secondary battery positive electrode according to claim 2, is characterized in that, the sintering temperature of described step 5 is 900 DEG C ~ 950 DEG C, and the time is 12 ~ 24 hours.
7. the sodium-ion battery for preparing of lithium base sodium ion secondary battery positive electrode according to claim 1.
CN201410765630.8A 2014-12-12 2014-12-12 Lithium-based positive electrode material for sodion secondary battery, preparation method of lithium-based positive electrode material and sodion battery Pending CN104466100A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111864200A (en) * 2020-08-25 2020-10-30 南开大学 High-capacity sodium ion battery positive electrode material
WO2020241713A1 (en) * 2019-05-27 2020-12-03 国立大学法人九州大学 Aqueous sodium ion secondary battery

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020241713A1 (en) * 2019-05-27 2020-12-03 国立大学法人九州大学 Aqueous sodium ion secondary battery
CN113939931A (en) * 2019-05-27 2022-01-14 国立大学法人九州大学 Aqueous sodium ion secondary battery
EP3978429A4 (en) * 2019-05-27 2023-06-28 Kyushu University, National University Corporation Aqueous sodium ion secondary battery
CN111864200A (en) * 2020-08-25 2020-10-30 南开大学 High-capacity sodium ion battery positive electrode material
CN111864200B (en) * 2020-08-25 2022-06-14 南开大学 High-capacity sodium ion battery positive electrode material

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Application publication date: 20150325