CN107611404A - A kind of white composite in Prussia and its preparation method and application - Google Patents
A kind of white composite in Prussia and its preparation method and application Download PDFInfo
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- CN107611404A CN107611404A CN201710826492.3A CN201710826492A CN107611404A CN 107611404 A CN107611404 A CN 107611404A CN 201710826492 A CN201710826492 A CN 201710826492A CN 107611404 A CN107611404 A CN 107611404A
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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 present invention discloses white composite in a kind of Prussia and its preparation method and application, preparation method, comprises the following steps：(1) sodium ferrocyanide or its hydrate are mixed to get solution A with deionized water, concentration is 0.1~0.5mol/L；Divalence Mn will be contained2+Soluble-salt mixed with deionized water, then fluorinated nano carbon pipe is added, through fully dispersed, obtains solution B, Mn in described solution B2+Concentration be 0.2~1.0mol/L；(3) solution B that step (2) obtains is added dropwise in the solution A for obtaining step (1), the described white composite in Prussia is obtained through hydro-thermal reaction and post processing.The white composite in Prussia prepared according to this method, application of the composite in sodium-ion battery.The preparation method of the present invention, has the advantages that technique is simple, cost is low, the cycle is short, energy consumption is low and suitable industrialized production.
Description
Technical field
The present invention relates to the technical field of novel energy storage cell, and in particular to a kind of white composite in Prussia and its preparation
Methods and applications.
Background technology
With society, expanding economy, energy resource consumption is increasingly aggravated, and traditional fossil energy is constantly reduced, and the mankind are to tradition
While the consumption of fossil energy, cause environmental pollution serious, it is cleaning, renewable, cheap new under this overall situation
The energy turn into national governments' exploitation to picture, the proportion of wind energy, solar energy and ocean energy in energy resource consumption is constantly increasing at present
Add, but these regenerative resources are had a great influence by weather and period, have obvious unstable, discontinuous and uncontrollable spy
Property is, it is necessary to the continuity developing and build supporting electrical power storage (energy storage) device i.e. battery to ensure to generate electricity, power and stably
Property, and large-scale battery energy storage is used for " peak load shifting " of electric power in power industry, it will significantly improve the confession of electric power
Contradiction is needed, improves the utilization rate of generating equipment.Requirement of the large-scale energy-storage battery to electrode material has certain energy density, longevity
Life, security it is also proposed higher requirement to cost outside having higher requirements.Although lead-acid battery cost is low, its raw material master
To be lead and sulfuric acid, exist easily pollution environment, service life make it is short, memory effect be present, battery weight greatly there is also transport into
This high problem；Although lithium ion battery has the advantages that energy density is big, service life is long and memory-less effect,
Lithium raw material reserves are limited, and lithium ion battery cost is high, and security performance is bad, in the long run, it is impossible to meets extensive energy storage
It is required that.Compared with lithium ion battery, sodium-ion battery aboundresources, have a safety feature, and it is low, environmentally friendly etc. with cost
Advantage, it is especially suitable for extensive stored energy application.
Some Prussian-blues are advantageous to the larger sodium ion of volume due to containing larger room in structure
Embedded and abjection, therefore capacity is higher, the material charging/discharging voltage particularly containing manganese is higher, is being adapted as sodium-ion battery just
Pole material.But this kind of compound is present, and electric conductivity is poor, tap density is low, causing to make battery needs to add many conductions
Agent, reduces the energy density of battery, while the addition of conductive agent, material tap density are low, and the processing characteristics of material can be poor.
In addition, this kind of compound is easily decomposed at high temperature, typically prepare at low temperature, synthesis temperature is less than 200 DEG C, therefore is prepared
The general crystallinity of ferrocyanide it is poor, and water content is higher, causes it to assemble to obtain sodium-ion battery as positive electrode
Capacity is relatively low, charging/discharging voltage is relatively low.Therefore, it is necessary to optimize preparation and with conductive material is compound improves its electrochemistry
Energy.
The content of the invention
The present invention discloses a kind of preparation method of the white composite in Prussia first, and this method can be to target product
Pattern and lattice structure are regulated and controled, and the white material in the Prussia being prepared has good crystallinity, low water content, high
Sodium content, it is applied in sodium-ion battery electrode, is remarkably improved the chemical property of sodium-ion battery, particularly capacity
And charging/discharging voltage.
The technology used in the present invention is as follows：A kind of preparation method of the white composite in Prussia, comprises the following steps：
(1) sodium ferrocyanide or its hydrate are mixed to get solution A with deionized water, concentration is 0.1~0.5mol/L；
(2) divalence Mn will be contained2+Soluble-salt mixed with deionized water, then by fluorinated nano carbon pipe add, through fully point
Dissipate, obtain solution B, Mn in described solution B2+Concentration be 0.2~1.0mol/L；
(3) solution B that step (2) obtains is added dropwise in the solution A for obtaining step (1), through hydro-thermal reaction and
Post processing obtains the described white composite in Prussia.
The present invention, due to suction-operated of the fluorine ion to manganese ion, can be dropped using fluorinated nano carbon pipe is introduced in synthesis
The speed of low coprecipitation reaction, the white crystallinity in Prussia, and the hydrophobic effect due to fluorographite and conductive author are improved, can
Reduce product crystal water content and improve electrical conductivity, so as to improve its capacity and charging/discharging voltage.Further, since fluorine ion and manganese
Ion or ferrous ion easily form coordinate bond, and its bonding action must cause composite to have good uniformity.
Preferably, the Oil repellent of fluorinated nano carbon pipe is 10~20%, Oil repellent is too low, is unfavorable for playing raising product
Crystallinity and the effect for reducing crystal water content, and improve the homogeneity of composite；Oil repellent is too high, and stone is fluorinated by reducing
The conductance of ink, so as to reduce the overall conductance of composite；
Preferably, the addition of fluorinated nano carbon pipe is the 4%~8% of the white materials theory weight in Prussia, excessive
Fluorinated nano carbon pipe adds the specific capacity that can reduce product；Too low fluorinated nano carbon pipe is added to improving product crystallinity, drop
Low crystal water content, the homogeneity for improving composite and raising electrical conductivity DeGrain；
Preferably, described soluble-salt is one or more of any mixed in its manganese chloride, manganese sulfate, manganese nitrate
Close, or any mixing of the one or more in hydrate corresponding to manganese chloride, manganese sulfate, manganese nitrate；
Preferably, Mn in soluble-salt in described solution B2+With the mol ratio of ferrous cyanide ion for 1.5~
2.5 very few Mn2+Mole is unfavorable for the crystalline perfection of product, excessive Mn2+Mole will cause the increasing of preparation cost
Add and the waste of raw material.
Preferably, the temperature of the hydro-thermal reaction is 70~90 DEG C；Hydrothermal temperature is too low, the white material knot in Prussia
It is brilliant imperfect, it is compound uneven with fluorinated nano carbon pipe；Reaction temperature is too high, and the water evaporation as reaction media is too fast, shadow
The formation of product is rung, and crystal water content is higher.Further preferably, the time of hydro-thermal reaction is 6~10h；Reaction time is too short,
The white material crystalline in Prussia is imperfect, sodium content is relatively low and crystal water content is higher；Reaction time is long, and product, which is crystallized, to be influenceed
Less, and can reduce synthesis efficiency increase prepare cost.
Product after hydro-thermal reaction also needs post-treated, including cools down, washs, vacuum drying treatment, wherein being dried in vacuo
Temperature is not less than 120 DEG C, and drying time is not less than 12 hours, and absorption water and zeolite can be effectively removed under this drying condition
Water, in addition, the bonding action of fluorine ion and manganese or ferrous ion will remove the part crystallization water in process of vacuum drying, therefore,
Product has relatively low water content, so as to have higher capacity.
The invention also discloses the white composite in a kind of Prussia prepared according to the above method, chemical formula is
NaxMnFe(CN)6·yH2O, in formula, x=1.6~2,0 ＜ y ＜ 1, it is known that, product has high sodium content and the low crystallization water
Content, high sodium content and low crystal water content can improve crystallinity, capacity and the charging/discharging voltage of product；Lattice structure
For rhombohedral phase, it is considered that, relative to Emission in Cubic, the crystal structure is advantageous to improve the capacity of product.
Products therefrom average charging tension is more than 3.8V, and average discharge volt is more than 3.6V, higher than the value of open report, with
Negative pole is engaged, and can be applied to high voltage sodium-ion battery.
Using the white material in Prussia that as above method is prepared, size is sub-micron in order irregular shape particle is presented
Level.Preferably, the size of the white material in Prussia is 300~500nm.The diffusion that particle is unfavorable for greatly very much sodium ion can drop
Low capacity, particle is too small to be unfavorable for electrode coating and reduces the energy density per unit volume metric density of battery.
Preferably, introducing fluorinated nano carbon pipe, the fluorine ion of fluorinated nano carbon pipe surface can attract Mn2+, reduce coprecipitated
Shallow lake reaction rate, so as to improve product crystallinity and capacity；The introducing of fluorinated nano carbon pipe can improve product electrical conductivity, so as to drop
The polarization of low electrode, improve battery operating voltage；In addition, the hydrophobicity of fluorinated nano carbon pipe can also reduce containing for the product crystallization water
Amount, so as to further improve product crystallinity, improve product capacity；Furthermore due to fluorine ion and manganese ion or ferrous ion key
Cooperation is used, and obtained composite has good uniformity.
Compared with prior art, the invention has the advantages that：
1st, present invention introduces fluorinated nano carbon pipe, to optimize the preparation of the white positive electrode in Prussia, the Pu Lu being prepared
There is high sodium content, relatively low crystal water content and good crystallinity and electric conductivity in the white positive electrode of scholar, using its as
The sodium-ion battery that positive electrode assembles to obtain has high power capacity and high charging/discharging voltage, so as to have high energy density.
2nd, preparation method of the invention, with technique is simple, cost is low, the cycle is short, energy consumption is low and suitable industrialized production
The advantages that.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum of the white composite in Prussia prepared by embodiment 1；
Fig. 2 is the stereoscan photograph of the white composite in Prussia prepared by embodiment 1；
Fig. 3 is the charging and discharging curve that the white composite in Prussia prepared with embodiment 1 assembles obtained sodium-ion battery
Figure.
Embodiment
Below according to Figure of description citing, the present invention will be further described：
Embodiment 1
Sodium ferrocyanide is dissolved in deionized water, being uniformly mixing to obtain the concentration in terms of ferrous cyanide ion is
0.1mol/L solution A；Protochloride manganese is dissolved in deionized water, obtained with Mn2+The solution that concentration is 0.2mol/L is counted, wherein
The mole of protochloride manganese is 1.5 times of sodium ferrocyanide, then adds fluorinated nano carbon pipe, and the Oil repellent of fluorinated nano carbon pipe is
15%, addition is the 6% of the white theoretical weight in Prussia, and solution B is obtained through abundant ultrasonic disperse；Then in the case where being stirred continuously,
Solution B is added dropwise in solution A, and through 80 DEG C of hydro-thermal reaction 10h, then through cooling down, washing, vacuum drying temperature is not less than
120 DEG C, drying time be not less than 12 hours after obtain the white composite in Prussia.
Fig. 1 is the X-ray diffraction spectrum of the white positive electrode in Prussia prepared by this implementation, and the material can be attributed to rhombohedral phase
Ferromanganic Cymag, CNT are not shown because content is low in figure.Fig. 2 is the white positive pole material in Prussia prepared by this implementation
The stereoscan photograph of material, understand that the white particle size in Prussia is 300~500nm from figure, fluorinated nano carbon pipe is in Prussia
It is dispersed in white particle.Through analysis, NaxMnFe(CN)6·yH2X is 1.75, y 0.97 in O.
Using the white composite in Prussia manufactured in the present embodiment as positive pole, using metallic sodium as negative pole, the glass fibre (trade mark
Whatman GF/D) it is barrier film, NaPF6Ethylene carbonate (EC)/diethyl carbonate (DEC) solution be electrolyte, full of
Battery is assembled in the glove box of argon gas, carries out charge-discharge test, charging and discharging curve is as shown in Figure 3.Constant current charge-discharge test (electricity
Current density 15mA/g, 2~4V of voltage range).It was found from figure, capacity is put down up to 146mAh/g, average discharge volt more than 3.6V
Bulk charge voltage is more than 3.8V.
Contrast 1
The preparation technology and embodiment 1 of the white positive electrode in Prussia are similar, except that not drawing in solution B
Enter CNT, other reaction conditions are identical.As a result show, because reaction rate is very fast, product is crystallized compared with the material containing carbon pipe
Material is poor, and due to no introducing CNT, product electric conductivity is poor, and crystal water content is high.Through analysis, NaxMnFe
(CN)6·yH2X ＜ 1.6 in O, y ＞ 2.
The white material in Prussia prepared using this comparative example is used as positive pole, using metallic sodium as negative pole, the glass fibre (trade mark
Whatman GF/D) it is barrier film, NaPF6EC/DEC solution be electrolyte, battery is assembled in the glove box full of argon gas, is entered
Row charge-discharge test.(current density 15mA/g, 2~4V of voltage range show that capacity is less than for constant current charge-discharge test
130mAh/g, and show relatively low charging/discharging voltage.
Contrast 2
The preparation technology and embodiment 1 of the white positive electrode in Prussia are similar, except that being introduced in solution B general
Logical CNT, other reaction conditions are identical.As a result show, because reaction rate is very fast, product crystallization relatively contains fluorinated nano
The material of carbon pipe is poor, and due to not having fluorine in CNT, crystal water content is high, and CNT is distributed in the white particle in Prussia
It is uneven.Through analysis, NaxMnFe(CN)6·yH2X ＜ 1.6 in O, y ＞ 2.
The white material in Prussia prepared using this comparative example is used as positive pole, using metallic sodium as negative pole, the glass fibre (trade mark
Whatman GF/D) it is barrier film, NaPF6EC/DEC solution be electrolyte, battery is assembled in the glove box full of argon gas, is entered
Row charge-discharge test.(current density 15mA/g, 2~4V of voltage range show that capacity is less than for constant current charge-discharge test
130mAh/g, and show relatively low charging/discharging voltage.
Comparative example 3
The preparation technology and embodiment 1 of the white positive electrode in Prussia are similar, except that introducing fluorine in solution B
Change the Oil repellent of CNT more than 40%, other reaction conditions are identical.As a result show, due to fluorinated volume in fluorinated nano carbon pipe
Too high, the electric conductivity of composite is poor, and the bonding of fluorine ion and manganese or ferrous ion is stronger, causes the electrochemistry of composite
Activity is relatively low.
The white material in Prussia prepared using this comparative example is used as positive pole, using metallic sodium as negative pole, the glass fibre (trade mark
Whatman GF/D) it is barrier film, NaPF6EC/DEC solution be electrolyte, battery is assembled in the glove box full of argon gas, is entered
Row charge-discharge test.(current density 15mA/g, 2~4V of voltage range show that capacity is less than for constant current charge-discharge test
120mAh/g, and show relatively low charging/discharging voltage.
Embodiment 2
Sodium ferrocyanide is dissolved in deionized water, being uniformly mixing to obtain the concentration in terms of ferrous cyanide ion is
0.15mol/L solution A；Manganese sulfate is dissolved in deionized water, obtained with Mn2+The solution that concentration is 0.3mol/L is counted, its
The mole of middle manganese sulfate is 2 times of sodium ferrocyanide, adds fluorinated nano carbon pipe, and addition is the white theoretical weight in Prussia
The 7% of amount, through being sufficiently stirred to obtain solution B；Then in the case where being stirred continuously, solution B is added dropwise in solution A, and through 90
DEG C hydro-thermal reaction 8h, then through cooling down, washing, vacuum drying temperature be not less than 120 DEG C, drying time be not less than 12 hours after obtain
The white composite in Prussia.XRD shows the ferromanganic Cymag that product is rhombohedral phase, and ESEM shows the white particle in Prussia
Size is 300~500nm, and fluorinated nano carbon pipe is dispersed in the white particle in Prussia, through analysis, NaxMnFe(CN)6·
yH2X is 1.72, y 0.87 in O.
Using the white composite in Prussia manufactured in the present embodiment as positive pole, using metallic sodium as negative pole, the glass fibre (trade mark
Whatman GF/D) it is barrier film, NaPF6EC/DEC solution is electrolyte, and battery is assembled in the glove box full of argon gas, is carried out
Charge-discharge test.Constant current charge-discharge test (current density 15mA/g, 2~4V of voltage range) shows that capacity is up to 144mAh/
G, average discharge volt is more than 3.6V, and average charging tension is more than 3.8V.
Embodiment 3
Sodium ferrocyanide is dissolved in deionized water, being uniformly mixing to obtain the concentration in terms of ferrous cyanide ion is
0.2mol/L solution A；Mn nitrate is dissolved in deionized water, obtained with Mn2+The solution that concentration is 0.4mol/L is counted, wherein
The mole of Mn nitrate is 2.5 times of sodium ferrocyanide, adds fluorinated nano carbon pipe, the Oil repellent of fluorinated nano carbon pipe is
10%, addition is the 5% of the white theoretical weight in Prussia, through being sufficiently stirred to obtain solution B；Then, will be molten in the case where being stirred continuously
Liquid B is added dropwise in solution A, and through 60 DEG C of hydro-thermal reaction 6h, then through cooling down, wash, after 120 DEG C of vacuum drying 12 hours
To the white composite in Prussia.XRD shows the ferromanganic Cymag that product is rhombohedral phase, and ESEM shows white in Prussia
Particle size is 300~500nm, and fluorinated nano carbon pipe is dispersed in the white particle in Prussia, through analysis, NaxMnFe(CN)6·
yH2X is 1.81, y 0.92 in O.
Using the white composite in Prussia manufactured in the present embodiment as positive pole, using metallic sodium as negative pole, the glass fibre (trade mark
Whatman GF/D) it is barrier film, NaPF6EC/DEC solution be electrolyte, battery is assembled in the glove box full of argon gas, is entered
Row charge-discharge test.Constant current charge-discharge test (current density 15mA/g, voltage range 2V~4V) shows that capacity is reachable
149mAh/g, average discharge volt is more than 3.6V, and average charging tension is more than 3.8V.
Embodiment 4
Sodium ferrocyanide is dissolved in deionized water, being uniformly mixing to obtain the concentration in terms of ferrous cyanide ion is
0.5mol/L solution A；Manganese sulfate is dissolved in deionized water, obtained with Mn2+The solution that concentration is 1.0mol/L is counted, wherein
The mole of manganese sulfate is 2.2 times of sodium ferrocyanide, adds fluorinated nano carbon pipe, the Oil repellent of fluorinated nano carbon pipe is
20%, addition is the 8% of the white theoretical weight in Prussia, through being sufficiently stirred to obtain solution B；Then, will be molten in the case where being stirred continuously
Liquid B is added dropwise in solution A, and through 90 DEG C of hydro-thermal reaction 10h, then through cooling down, washing, vacuum drying temperature is not less than 120
DEG C, drying time be not less than 12 hours after obtain the white composite in Prussia.XRD shows the ferromanganic cyaniding that product is rhombohedral phase
Sodium, ESEM show that the white particle size in Prussia is 300~500nm, and fluorinated nano carbon pipe is equal in the white particle in Prussia
It is even scattered, through analysis, NaxMnFe(CN)6·yH2X is 1.77, y 0.93 in O.
Using the white composite in Prussia manufactured in the present embodiment as positive pole, using metallic sodium as negative pole, the glass fibre (trade mark
Whatman GF/D) it is barrier film, NaPF6EC/DEC solution be electrolyte, battery is assembled in the glove box full of argon gas, is entered
Row charge-discharge test.Constant current charge-discharge test (current density 15mA/g, voltage range 2V~4V) shows that capacity is reachable
149mAh/g, average discharge volt is more than 3.6V, and average charging tension is more than 3.8V.
Claims (10)
1. a kind of preparation method of the white composite in Prussia, it is characterised in that comprise the following steps：
(1) sodium ferrocyanide or its hydrate are mixed to get solution A with deionized water, concentration is 0.1~0.5mol/L；
(2) divalence Mn will be contained2+Soluble-salt mixed with deionized water, then fluorinated nano carbon pipe is added, through fully dispersed, obtained
To solution B, Mn in described solution B2+Concentration be 0.2~1.0mol/L；
(3) solution B that step (2) obtains is added dropwise in the solution A for obtaining step (1), through hydro-thermal reaction and after locate
Reason obtains the described white composite in Prussia.
2. the preparation method of the white composite in Prussia according to claim 1, it is characterised in that described fluorinated nano
The Oil repellent of carbon pipe is 10~20%.
3. the preparation method of the white composite in Prussia according to claim 1, it is characterised in that fluorinated nano carbon pipe
Addition is the 4%~8% of the white composite weight in the Prussia finally obtained.
4. the preparation method of the white composite in Prussia according to claim 1, it is characterised in that described soluble-salt
For any mixing of one or more in its manganese chloride, manganese sulfate, manganese nitrate, or water corresponding to manganese chloride, manganese sulfate, manganese nitrate
Any mixing of one or more in compound.
5. the preparation method of the white composite in Prussia according to claim 1, it is characterised in that in described solution B
Mn2+Be 1.5~2.5 with the mol ratio of ferrous cyanide ion.
6. the preparation method of the white composite in Prussia according to claim 1, it is characterised in that the hydro-thermal reaction
Temperature is 70~90 DEG C, and the reaction time is 6~10h.
7. the preparation method of the white composite in Prussia according to claim 1, it is characterised in that the production after hydro-thermal reaction
Thing is also needed to cool down, washed, vacuum drying treatment, and wherein vacuum drying temperature is not less than 120 DEG C, and drying time is small not less than 12
When.
A kind of 8. white composite in Prussia prepared by method according to any one of claim 1~7, it is characterised in that
The white chemical formula in Prussia is NaxMnFe(CN)6·yH2O, in formula, x=1.6~2,0 ＜ y ＜ 1；Lattice structure is rhombohedral phase.
9. the white composite in Prussia prepared by a kind of method according to any one of claim 1~7 claim is in sodium
Application in ion battery, average charging tension is more than 3.8V, and average discharge volt is more than 3.6V.
10. the white composite in Prussia according to claim 8, it is characterised in that the white material in described Prussia is presented
Irregular shape, size are 300~500nm, and fluorinated nano carbon pipe is dispersed in the white material in Prussia, fluorine ion and manganese from
Son or ferrous ion can be bonded, and form uniform composite.
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| CN108821310A (en) * | 2018-05-25 | 2018-11-16 | 浙江大学 | One white material in type Prussia and its preparation method and application |
| CN108821311A (en) * | 2018-06-21 | 2018-11-16 | 福州大学 | A kind of preparation method of the fine white mesomorphic material in adjustable Prussia of manganese iron component |
| CN109065847A (en) * | 2018-05-25 | 2018-12-21 | 浙江大学 | A kind of white composite material and preparation method in Prussia and application |
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| CN110085819A (en) * | 2019-04-16 | 2019-08-02 | 浙江大学 | One kind mixing sodium potassium base cyaniding frame composite material and its preparation method and application |
| CN110165167A (en) * | 2019-05-14 | 2019-08-23 | 上海汉行科技有限公司 | Modified ferrocyanogen material in a kind of surface and preparation method thereof |
| WO2020040338A1 (en) * | 2018-08-21 | 2020-02-27 | 전자부품연구원 | Positive electrode material, positive electrode and sodium-ion battery comprising same, and preparation method therefor |
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| CN111252784A (en) * | 2020-01-22 | 2020-06-09 | 浙江凯恩电池有限公司 | Preparation method of manganese-based Prussian white positive electrode material and application of manganese-based Prussian white positive electrode material in sodium-ion battery electrode |
| CN112786828A (en) * | 2021-02-22 | 2021-05-11 | 宁波容百新能源科技股份有限公司 | Prussian positive plate with high compaction density and high rate performance, preparation method of prussian positive plate and sodium ion battery |
| CN114212803A (en) * | 2021-10-28 | 2022-03-22 | 广东邦普循环科技有限公司 | Preparation method of fluorine-doped Prussian blue type sodium ion battery positive electrode material |
| CN115321557A (en) * | 2022-10-14 | 2022-11-11 | 江苏智纬电子科技有限公司 | Prussian white composite material for sodium ion battery and preparation method thereof |
| US11824194B2 (en) | 2019-08-07 | 2023-11-21 | Tsinghua University | Method for rapidly preparing Prussian blue analogue with monoclinic crystal structure |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010059041A (en) * | 2008-09-04 | 2010-03-18 | Korea Inst Of Science & Technology | Transition metal oxide/multi-walled carbon nanotube nanocomposite and method for manufacturing the same |
| US20130157135A1 (en) * | 2010-09-10 | 2013-06-20 | Mingjie Zhou | Lithium salt-graphene-containing composite material and preparation method thereof |
| CN104247131A (en) * | 2012-04-17 | 2014-12-24 | 夏普株式会社 | Alkali and alkaline-earth ion batteries with hexacyanometallate cathode and non-metal anode |
| CN106469828A (en) * | 2016-12-12 | 2017-03-01 | 华中科技大学 | A kind of graphite/Prussian blue composite material and preparation method thereof and its application |
| CN106549155A (en) * | 2016-10-20 | 2017-03-29 | 河南师范大学 | A kind of potassium sodium ferromanganese base prussian blue electrode material and its preparation method and application |
-
2017
- 2017-09-14 CN CN201710826492.3A patent/CN107611404B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010059041A (en) * | 2008-09-04 | 2010-03-18 | Korea Inst Of Science & Technology | Transition metal oxide/multi-walled carbon nanotube nanocomposite and method for manufacturing the same |
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