CN106654263A - Preparation method of Prussian blue based sodium ion battery positive electrode material - Google Patents
Preparation method of Prussian blue based sodium ion battery positive electrode material Download PDFInfo
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- CN106654263A CN106654263A CN201611255163.XA CN201611255163A CN106654263A CN 106654263 A CN106654263 A CN 106654263A CN 201611255163 A CN201611255163 A CN 201611255163A CN 106654263 A CN106654263 A CN 106654263A
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- prussian blue
- sodium
- ion battery
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- battery positive
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/08—Simple or complex cyanides of metals
- C01C3/12—Simple or complex iron cyanides
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a Prussian blue based sodium ion battery positive electrode material. The preparation method takes ferrous oxalate and sodium oxalate as raw materials, and makes the raw materials react with sodium ferrocyanide; a reaction speed can be slower and the production speed of a Prussian blue mono-crystal becomes slow, so that the aim of reducing defects in a Prussian blue crystal is realized. A sodium ion battery positive electrode prepared from the Prussian blue crystal can still keep good stability after being subjected to a plurality of times of charge-discharge cycles, and the service life is long. The method is simple in preparation process, easy to implement and suitable for large-scale production.
Description
Technical field
The present invention relates to field of batteries, more particularly to a kind of preparation side of Prussian blue base sodium-ion battery positive material
Method.
Background technology
With the fast development of extensive intelligent grid, and the popularization and application of electric automobile, lithium resource cannot meet lithium
The great demand of ion battery, the energy storage technology for developing alternative lithium ion battery is extremely necessary.Sodium reserves in the earth's crust are rich
Richness, it is widely distributed, belong to congenerss with lithium, it is a kind of battery raw material of feasible replacement lithium.But sodium atom amount is bigger than lithium,
Standard electrochemical potential is lower than lithium, and current sodium-ion battery energy density is also difficult to be compared favourably with lithium ion battery, and it is right to still need to
Sodium-ion battery system is studied.
Sodium-ion battery is made up of positive pole, negative pole, electrolyte and barrier film etc.：The usual employing of positive and negative electrode material can be embedded in/
The active material of deintercalation sodium ion, electrolyte is then made up of sodium ion conducting salt and organic solvent.The active matter of positive and negative electrode material
Matter is electrochemically reacted, and determines the fundamental characteristics of this electrode, is the core component of sodium-ion battery, and the performance of battery is played
Important function.The at present research with regard to sodium ion positive electrode be concentrated mainly on transition metal oxide, polyanionic compound,
Six cyanogen metallic compounds or organic-based material etc..Wherein Prussian blue (KFe [Fe (CN)6]) there is three-dimensional open architecture, have
It is a kind of typical transition metal iron cyanide beneficial to the transmission and storage of alkali metal ion.It is Prussian blue in water system battery
The electrochemical behavior of excellent K and Na is shown, its excellent chemical property shows good in large-scale energy storage device
Good application prospect.
Chinese patent CN201510097071.2 discloses a kind of sodium-ion battery richness sodium positive electrode and preparation method thereof
With a kind of sodium-ion battery, the method comprising the steps of：(1) under agitation, it is nickel salt solution, cobalt salt solution, manganese salt is molten
Liquid, oxalate solution and sodium salt solution mixing, the condition of the mixing causes Ni2+, Co2+, Mn2+ and Na+ in mixed solution
Total mole number is 0.8～1 with the ratio of the molal quantity of oxalate denominationby：1；(2) in a sealed meter environment, above-mentioned mixed solution is carried out
Hydro-thermal reaction, then cooled down, solid-liquid separation, washing, drying, obtain presoma；(3) presoma is forged under air atmosphere
Burn, obtain sodium-ion battery richness sodium positive electrode.The sodium-ion battery richness sodium positive electrode that the inventive method is prepared can
The high power capacity discharge and recharge of sodium-ion battery is realized, and makes sodium-ion battery that there is excellent cyclical stability.
The content of the invention
It is an object of the invention to provide a kind of preparation method of Prussian blue base sodium-ion battery positive material, party's legal system
Standby Prussian blue defect is little, good cycling stability, so as to the positive electrode capacity dimension for preparing holds efficiency high, long service life.
For achieving the above object, the present invention is employed the following technical solutions：
A kind of preparation method of Prussian blue base sodium-ion battery positive material, comprises the following steps：
(1) by after Ferrox. and Disodium oxalate. mix homogeneously, in solution and water, surfactant is added, ultrasonic agitation is equal
It is even, and after froth breaking, be added dropwise to ferrocyanide sodium water solution wherein using peristaltic pump, at ambient temperature, with 120-
The speed stirring of 300rpm, after completion of dropping, continues to stir 36-48h, and blue precipitate is obtained, by its deionized water centrifugation
After cleaning repeatedly, using absolute ethanol washing 2-3 time, afterwards evacuation is dried, prepared Prussian blue；
(2) after by obtained Prussian blue, conductive agent mixing, it is placed in marble and grinds in tank, and is added thereto to deionization
Water, adds zirconium dioxide mill ball, with 200-450rpm rotational speeds, after obtained powder is dried, is scattered in dehydrated alcohol
In, after Deca binding agent mix homogeneously, vacuum drying, after tabletting, as described positive electrode.
Preferably, the use mol ratio of the Ferrox. and Disodium oxalate. is 1-2:1；Ferrox. and surfactant
Use quality amount is than position 1.5-2:1；Ferrox. is 1 with the mol ratio that sodium ferrocyanide is used：2.2-2.5.
Preferably, the surfactant is P123, fatty alcohol-polyoxyethylene ether, sodium stearoyl lactate or dodecyl sulfur
One kind in sour sodium.
Preferably, the ball milling pearl is zirconium oxide spheroidal graphite pearl, and diameter is respectively 2mm, and 1mm's waits mass mixing thing.
Preferably, the process of lapping persistent period be 10-12h, during every half an hour convert direction of rotation.
Preferably, the conductive agent is the one kind in acetylene black, CNT, carbon nano-fiber or expanded graphite.
Preferably, described adhesive is in polyvinylidene fluoride, polrvinyl chloride polyvinyl alcohol or Carboxymethyl cellulose sodium
It is a kind of.
Preferably, in the step (2), the input amount of each component is Prussian blue 65-80 parts, conductive agent 15-25 parts, two
Zirconium oxide abrasive ball 80-105 parts, binding agent 5-10 parts.
The invention has the advantages that, Ferrox. and Disodium oxalate. are adopted for raw material, react with sodium ferrocyanide, can
So that response speed is slower so that the speed of production of Prussian blue monocrystalline is slack-off, so as to reduce Prussian blue crystal
In defect purpose.The sodium-ion battery positive pole prepared by the Prussian blue crystal, remains to after multiple charge and discharge cycles
Keep good stability, long service life.And the method preparation process is simple, easily with enforcement, it is adapted to large-scale production.
Specific embodiment
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solution
The present invention is released, any restriction will not be constituted to the present invention.
Embodiment 1
A kind of preparation method of Prussian blue base sodium-ion battery positive material, comprises the following steps：
(1) by after Ferrox. and Disodium oxalate. mix homogeneously, in solution and water, surfactant is added, ultrasonic agitation is equal
It is even, and after froth breaking, be added dropwise to ferrocyanide sodium water solution wherein using peristaltic pump, at ambient temperature, with 120rpm's
Speed stir, after completion of dropping, continue stir 36h, be obtained blue precipitate, by its deionized water eccentric cleaning it is multiple after,
Using absolute ethanol washing 2 times, afterwards evacuation is dried, and is obtained Prussian blue；
(2) after by obtained Prussian blue, conductive agent mixing, it is placed in marble and grinds in tank, and is added thereto to deionization
Water, adds zirconium dioxide mill ball, with 200rpm rotational speeds, after obtained powder is dried, and in being scattered in dehydrated alcohol, drop
Plus after binding agent mix homogeneously, vacuum drying, after tabletting, as described positive electrode.
The use mol ratio of Ferrox. and Disodium oxalate. is 1:1；The use quality amount ratio of Ferrox. and surfactant
Position 1.5:1；Ferrox. is 1 with the mol ratio that sodium ferrocyanide is used：2.2.Surfactant is P123, fatty alcohol polyoxy second
One kind in alkene ether, sodium stearoyl lactate or sodium lauryl sulphate.Ball milling pearl is zirconium oxide spheroidal graphite pearl, and diameter is respectively 2mm,
1mm's waits mass mixing thing.The process of lapping persistent period be 10-12h, during every half an hour convert direction of rotation.It is conductive
Agent is the one kind in acetylene black, CNT, carbon nano-fiber or expanded graphite.Binding agent is polyvinylidene fluoride, polychlorostyrene second
One kind in alkene polyvinyl alcohol or Carboxymethyl cellulose sodium.In step (2), the input amount of each component is Prussian blue 65 parts, is led
15 parts of electric agent, 80 parts of zirconium dioxide mill ball, 5 parts of binding agent.
Embodiment 2
A kind of preparation method of Prussian blue base sodium-ion battery positive material, comprises the following steps：
(1) by after Ferrox. and Disodium oxalate. mix homogeneously, in solution and water, surfactant is added, ultrasonic agitation is equal
It is even, and after froth breaking, be added dropwise to ferrocyanide sodium water solution wherein using peristaltic pump, at ambient temperature, with 300rpm's
Speed stir, after completion of dropping, continue stir 48h, be obtained blue precipitate, by its deionized water eccentric cleaning it is multiple after,
Using absolute ethanol washing 3 times, afterwards evacuation is dried, and is obtained Prussian blue；
(2) after by obtained Prussian blue, conductive agent mixing, it is placed in marble and grinds in tank, and is added thereto to deionization
Water, adds zirconium dioxide mill ball, with 450rpm rotational speeds, after obtained powder is dried, and in being scattered in dehydrated alcohol, drop
Plus after binding agent mix homogeneously, vacuum drying, after tabletting, as described positive electrode.
The use mol ratio of Ferrox. and Disodium oxalate. is 2:1；The use quality amount ratio of Ferrox. and surfactant
Position 2:1；Ferrox. is 1 with the mol ratio that sodium ferrocyanide is used:2.5.Surfactant is P123, aliphatic alcohol polyethenoxy
One kind in ether, sodium stearoyl lactate or sodium lauryl sulphate.Ball milling pearl is zirconium oxide spheroidal graphite pearl, and diameter is respectively 2mm,
1mm's waits mass mixing thing.The process of lapping persistent period be 12h, during every half an hour convert direction of rotation.Conductive agent is
One kind in acetylene black, CNT, carbon nano-fiber or expanded graphite.Binding agent is polyvinylidene fluoride, polrvinyl chloride gathers
One kind in vinyl alcohol or Carboxymethyl cellulose sodium.In step (2), the input amount of each component is Prussian blue 80 parts, conductive agent
25 parts, 105 parts of zirconium dioxide mill ball, 10 parts of binding agent.
Embodiment 3
A kind of preparation method of Prussian blue base sodium-ion battery positive material, comprises the following steps：
(1) by after Ferrox. and Disodium oxalate. mix homogeneously, in solution and water, surfactant is added, ultrasonic agitation is equal
It is even, and after froth breaking, be added dropwise to ferrocyanide sodium water solution wherein using peristaltic pump, at ambient temperature, with 200rpm's
Speed stir, after completion of dropping, continue stir 40h, be obtained blue precipitate, by its deionized water eccentric cleaning it is multiple after,
Using absolute ethanol washing 2 times, afterwards evacuation is dried, and is obtained Prussian blue；
(2) after by obtained Prussian blue, conductive agent mixing, it is placed in marble and grinds in tank, and is added thereto to deionization
Water, adds zirconium dioxide mill ball, with 350rpm rotational speeds, after obtained powder is dried, and in being scattered in dehydrated alcohol, drop
Plus after binding agent mix homogeneously, vacuum drying, after tabletting, as described positive electrode.
The use mol ratio of Ferrox. and Disodium oxalate. is 1:1；The use quality amount ratio of Ferrox. and surfactant
Position 2:1；Ferrox. is 1 with the mol ratio that sodium ferrocyanide is used：2.4.Surfactant is P123, aliphatic alcohol polyethenoxy
One kind in ether, sodium stearoyl lactate or sodium lauryl sulphate.Ball milling pearl is zirconium oxide spheroidal graphite pearl, and diameter is respectively 2mm,
1mm's waits mass mixing thing.The process of lapping persistent period be 11h, during every half an hour convert direction of rotation.Conductive agent is
One kind in acetylene black, CNT, carbon nano-fiber or expanded graphite.Binding agent is polyvinylidene fluoride, polrvinyl chloride gathers
One kind in vinyl alcohol or Carboxymethyl cellulose sodium.In step (2), the input amount of each component is Prussian blue 70 parts, conductive agent
20 parts, 90 parts of zirconium dioxide mill ball, 8 parts of binding agent.Embodiment 4
A kind of preparation method of Prussian blue base sodium-ion battery positive material, comprises the following steps：
(1) by after Ferrox. and Disodium oxalate. mix homogeneously, in solution and water, surfactant is added, ultrasonic agitation is equal
It is even, and after froth breaking, be added dropwise to ferrocyanide sodium water solution wherein using peristaltic pump, at ambient temperature, with 200rpm's
Speed stir, after completion of dropping, continue stir 40h, be obtained blue precipitate, by its deionized water eccentric cleaning it is multiple after,
Using absolute ethanol washing 3 times, afterwards evacuation is dried, and is obtained Prussian blue；
(2) after by obtained Prussian blue, conductive agent mixing, it is placed in marble and grinds in tank, and is added thereto to deionization
Water, adds zirconium dioxide mill ball, with 350rpm rotational speeds, after obtained powder is dried, and in being scattered in dehydrated alcohol, drop
Plus after binding agent mix homogeneously, vacuum drying, after tabletting, as described positive electrode.
The use mol ratio of Ferrox. and Disodium oxalate. is 2:1；The use quality amount ratio of Ferrox. and surfactant
Position 1.5:1；Ferrox. is 1 with the mol ratio that sodium ferrocyanide is used：2.2.Surfactant is P123, fatty alcohol polyoxy second
One kind in alkene ether, sodium stearoyl lactate or sodium lauryl sulphate.Ball milling pearl is zirconium oxide spheroidal graphite pearl, and diameter is respectively 2mm,
1mm's waits mass mixing thing.The process of lapping persistent period be 12h, during every half an hour convert direction of rotation.Conductive agent is
One kind in acetylene black, CNT, carbon nano-fiber or expanded graphite.Binding agent is polyvinylidene fluoride, polrvinyl chloride gathers
One kind in vinyl alcohol or Carboxymethyl cellulose sodium.In step (2), the input amount of each component is Prussian blue 70 parts, conductive agent
22 parts, 95 parts of zirconium dioxide mill ball, 7 parts of binding agent.
Embodiment 5
A kind of preparation method of Prussian blue base sodium-ion battery positive material, comprises the following steps：
(1) by after Ferrox. and Disodium oxalate. mix homogeneously, in solution and water, surfactant is added, ultrasonic agitation is equal
It is even, and after froth breaking, be added dropwise to ferrocyanide sodium water solution wherein using peristaltic pump, at ambient temperature, with 180rpm's
Speed stir, after completion of dropping, continue stir 45h, be obtained blue precipitate, by its deionized water eccentric cleaning it is multiple after,
Using absolute ethanol washing 2 times, afterwards evacuation is dried, and is obtained Prussian blue；
(2) after by obtained Prussian blue, conductive agent mixing, it is placed in marble and grinds in tank, and is added thereto to deionization
Water, adds zirconium dioxide mill ball, with 350rpm rotational speeds, after obtained powder is dried, and in being scattered in dehydrated alcohol, drop
Plus after binding agent mix homogeneously, vacuum drying, after tabletting, as described positive electrode.
The use mol ratio of Ferrox. and Disodium oxalate. is 1:1；The use quality amount ratio of Ferrox. and surfactant
Position 1.8:1；Ferrox. is 1 with the mol ratio that sodium ferrocyanide is used：2.4.Surfactant is P123, fatty alcohol polyoxy second
One kind in alkene ether, sodium stearoyl lactate or sodium lauryl sulphate.Ball milling pearl is zirconium oxide spheroidal graphite pearl, and diameter is respectively 2mm,
1mm's waits mass mixing thing.The process of lapping persistent period be 12h, during every half an hour convert direction of rotation.Conductive agent is
One kind in acetylene black, CNT, carbon nano-fiber or expanded graphite.Binding agent is polyvinylidene fluoride, polrvinyl chloride gathers
One kind in vinyl alcohol or Carboxymethyl cellulose sodium.In step (2), the input amount of each component is Prussian blue 65 parts, conductive agent
18 parts, 95 parts of zirconium dioxide mill ball, 6 parts of binding agent.
Claims (8)
1. a kind of preparation method of Prussian blue base sodium-ion battery positive material, comprises the following steps：
(1) by after Ferrox. and Disodium oxalate. mix homogeneously, in solution and water, surfactant is added, ultrasonic agitation is uniform, and
And after froth breaking, be added dropwise to ferrocyanide sodium water solution wherein using peristaltic pump, at ambient temperature, with the speed of 120-300rpm
Degree stirring, after completion of dropping, continue stir 36-48h, be obtained blue precipitate, by its deionized water eccentric cleaning it is multiple after,
Using absolute ethanol washing 2-3 time, afterwards evacuation is dried, and is obtained Prussian blue；
(2) after by obtained Prussian blue, conductive agent mixing, it is placed in marble and grinds in tank, and is added thereto to deionized water, plus
Enter zirconium dioxide mill ball, with 200-450rpm rotational speeds, after obtained powder is dried, in being scattered in dehydrated alcohol, drop
Plus after binding agent mix homogeneously, vacuum drying, after tabletting, as described positive electrode.
2. the preparation method of Prussian blue base sodium-ion battery positive material according to claim 1, it is characterised in that：Institute
The use mol ratio for stating Ferrox. and Disodium oxalate. is 1-2:1；The use quality amount of Ferrox. and surfactant compares position
1.5-2:1；Ferrox. is 1 with the mol ratio that sodium ferrocyanide is used:2.2-2.5.
3. the preparation method of Prussian blue base sodium-ion battery positive material according to claim 1, it is characterised in that：Institute
Surfactant is stated for P123, fatty alcohol-polyoxyethylene ether, the one kind in sodium stearoyl lactate or sodium lauryl sulphate.
4. the preparation method of Prussian blue base sodium-ion battery positive material according to claim 1, it is characterised in that：Institute
It is zirconium oxide spheroidal graphite pearl to state ball milling pearl, and diameter is respectively 2mm, and 1mm's waits mass mixing thing.
5. the preparation method of Prussian blue base sodium-ion battery positive material according to claim 1, it is characterised in that：Institute
The process of lapping persistent period is stated for 10-12h, during convert direction of rotation every half an hour.
6. the preparation method of Prussian blue base sodium-ion battery positive material according to claim 1, it is characterised in that：Institute
Conductive agent is stated for the one kind in acetylene black, CNT, carbon nano-fiber or expanded graphite.
7. the preparation method of Prussian blue base sodium-ion battery positive material according to claim 1, it is characterised in that：Institute
Binding agent is stated for the one kind in polyvinylidene fluoride, polrvinyl chloride polyvinyl alcohol or Carboxymethyl cellulose sodium.
8. the preparation method of Prussian blue base sodium-ion battery positive material according to claim 1, it is characterised in that：Institute
In stating step (2), the input amount of each component is Prussian blue 65-80 parts, conductive agent 15-25 parts, zirconium dioxide mill ball 80-
105 parts, binding agent 5-10 parts.
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| CN201611255163.XA CN106654263A (en) | 2016-12-30 | 2016-12-30 | Preparation method of Prussian blue based sodium ion battery positive electrode material |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107331864A (en) * | 2017-06-21 | 2017-11-07 | 浙江大学 | A kind of cyano group positive electrode and its preparation method and application |
| CN108821310A (en) * | 2018-05-25 | 2018-11-16 | 浙江大学 | One white material in type Prussia and its preparation method and application |
| CN109637813A (en) * | 2018-11-12 | 2019-04-16 | 华东师范大学 | A kind of sunlight helps seawater battery and preparation method |
| CN109638241A (en) * | 2018-11-30 | 2019-04-16 | 张五星 | Ultra-fine iron-based Prussian blue and the like, preparation method and sodium-ion battery |
| CN109728295A (en) * | 2017-10-30 | 2019-05-07 | 宁德时代新能源科技股份有限公司 | Positive active material, preparation method thereof and sodium ion battery |
| CN114709402A (en) * | 2022-04-21 | 2022-07-05 | 温州大学碳中和技术创新研究院 | Preparation and application of carbon-coated sodiumsulverine-based Prussian blue positive electrode material |
| CN114940502A (en) * | 2022-07-26 | 2022-08-26 | 鸿兴(山西)新能源材料有限公司 | Production method and device of manganese-based prussian white |
| WO2023071352A1 (en) * | 2021-10-26 | 2023-05-04 | 广东邦普循环科技有限公司 | Preparation method for prussian blue sodium-ion battery positive electrode material |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107331864A (en) * | 2017-06-21 | 2017-11-07 | 浙江大学 | A kind of cyano group positive electrode and its preparation method and application |
| CN107331864B (en) * | 2017-06-21 | 2019-10-18 | 浙江大学 | A kind of cyano positive electrode and its preparation method and application |
| CN114335518A (en) * | 2017-10-30 | 2022-04-12 | 宁德时代新能源科技股份有限公司 | Positive active material, preparation method thereof and sodium ion battery |
| CN109728295A (en) * | 2017-10-30 | 2019-05-07 | 宁德时代新能源科技股份有限公司 | Positive active material, preparation method thereof and sodium ion battery |
| CN108821310A (en) * | 2018-05-25 | 2018-11-16 | 浙江大学 | One white material in type Prussia and its preparation method and application |
| CN108821310B (en) * | 2018-05-25 | 2020-04-14 | 浙江大学 | Prussian-like white material and preparation method and application thereof |
| CN109637813A (en) * | 2018-11-12 | 2019-04-16 | 华东师范大学 | A kind of sunlight helps seawater battery and preparation method |
| CN109638241A (en) * | 2018-11-30 | 2019-04-16 | 张五星 | Ultra-fine iron-based Prussian blue and the like, preparation method and sodium-ion battery |
| CN109638241B (en) * | 2018-11-30 | 2021-07-23 | 张五星 | Superfine iron-based Prussian blue and analogue thereof, preparation method and sodium ion battery |
| WO2023071352A1 (en) * | 2021-10-26 | 2023-05-04 | 广东邦普循环科技有限公司 | Preparation method for prussian blue sodium-ion battery positive electrode material |
| GB2620324A (en) * | 2021-10-26 | 2024-01-03 | Guangdong Brunp Recycling Technology Co Ltd | Preparation method for Prussian blue sodium-ion battery positive electrode material |
| CN114709402A (en) * | 2022-04-21 | 2022-07-05 | 温州大学碳中和技术创新研究院 | Preparation and application of carbon-coated sodiumsulverine-based Prussian blue positive electrode material |
| CN114940502A (en) * | 2022-07-26 | 2022-08-26 | 鸿兴(山西)新能源材料有限公司 | Production method and device of manganese-based prussian white |
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Application publication date: 20170510 |