CN109742398A - The synthesis and application method of a kind of lithium ion battery with manganese systems Prussian blue analogue material - Google Patents
The synthesis and application method of a kind of lithium ion battery with manganese systems Prussian blue analogue material Download PDFInfo
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- CN109742398A CN109742398A CN201910013396.6A CN201910013396A CN109742398A CN 109742398 A CN109742398 A CN 109742398A CN 201910013396 A CN201910013396 A CN 201910013396A CN 109742398 A CN109742398 A CN 109742398A
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Abstract
The synthesis and application method of a kind of lithium ion battery with manganese systems Prussian blue analogue material, belong to preparation and the application method of manganese systems Prussian blue analogue material.Step: manganese source is selected from anhydrous Manganese chloride (MnCl2) or a chloride hydrate manganese (MnCl2·H2O)；Source of iron and cyanogen root are selected from the potassium ferricyanide (K3[Fe(CN)6])；Chelating agent selects anhydrous citric acid sodium or trisodium citrate dihydrate；Manganese source and chelating agent x:1 in mass ratio weighing are dissolved in the methanol and deionized water mixed solution of arbitrary proportion, solution A is configured to；The potassium ferricyanide is dissolved in deionized water, is configured to the solution B that concentration is 0.04mol/L；Solution B is poured into solution A, is uniformly mixed, obtains solution C, 6-24 hours static at room temperature, separating-purifying and drying can be obtained target product.Advantage: raw material is easy to get, and synthetic method is simple, and operating procedure controllability is high, and products obtained therefrom purity is high, uniform particle diameter, and structure is hollow cube, is easy to large scale preparation.As lithium ion battery negative material electrochemical performance.
Description
Technical field
The present invention relates to a kind of preparation of manganese systems Prussian blue analogue material and application method, especially a kind of lithium ion battery
Synthesis and application method with manganese systems Prussian blue analogue material.
Background technique
Energy problem is the indispensable part of nowadays social development.The traditional fossil energies such as petroleum, coal are due to having
Pollution problem in non-renewable and use process, becomes the problem that nowadays social development is faced, thus using and hair
Renewable resource is opened up, component new energy pattern becomes the inexorable trend of social development.But solar energy, tide energy etc. clean
The energy has the defects of source is unstable and obvious by territory restriction, to can not efficiently apply to actual production, in life.Cause
This, the development of scale energy storage technology also becomes inexorable trend, and exploitation service life length, capacity height, good cycle, safety are without dirt
The new type of energy storage device of dye attracts wide attention.In existing energy storage technology, electrochemical energy storage technology becomes Developing mainstream.
Lithium ion battery has many advantages, such as that voltage is high, energy density is high, functional density is high, self discharge is small and is sent out rapidly
Exhibition, is used widely in portable energy-storing field.Negative electrode material is the critical material of lithium ion battery energy storage, currently, graphite
Sill has been realized in industrialization as lithium ion battery negative material, but in view of the limited theoretical capacity of graphite material and compared with
The cyclical stability of difference, now needs to seek and develop the novel anode material of height ratio capacity.
It is Prussian blue and the like in recent years in fields such as electrode ornament materials, energy storage compared to traditional negative electrode material
Show up prominently.Currently, using Prussian blue material as the inorganic-organic material of representative, have special three-dimensional open frame structure and
Nano-porous structure is suitble to receiving and the fast transferring of alkali metal ion, has excellent cycle life, thus as great
The electrode material of potentiality becomes research hotspot.
Prussian blue analogue material, because its raw material sources are extensive, adjustability is strong, sustainable development has due to the advantages that
There is the important research value as electrode material.It is numerous studies have shown that the microscopic appearance of material will affect or even determine its
Performance in practical application.
Tradition is prepared in Prussian blue similar object technique, and two-step synthesis method is generally used, and first forming core growth obtains solid vertical
The Prussian blue similar object of cube pattern, then the microscopic appearance for obtaining hollow out is etched by soda acid.
Summary of the invention
The invention aims to provide a kind of raw material to be easy to get, the lithium ion battery manganese systems Prussian blue analogue of method simplicity
The synthesis of material and application method.
The object of the present invention is achieved like this: reactant concentration, reaction time technical parameter in regulation reaction process lead to
One-step synthesis is crossed, realizes the synthesis quick, cheap to manganese systems Prussian blue analogue material, and can be with the micro- of stability contorting material
Partial size and degree of hollowness are seen, using manganese systems Prussian blue analogue material as the negative electrode material of lithium ion battery.
Manganese systems Prussian blue analogue control of material synthesis, comprising the following steps:
Manganese source is selected from anhydrous Manganese chloride (MnCl2) or a chloride hydrate manganese (MnCl2·H2O)；
Source of iron and cyanogen root are selected from the potassium ferricyanide (K3[Fe(CN)6])；
Chelating agent selects anhydrous citric acid sodium or trisodium citrate dihydrate；
Manganese source and chelating agent x:1 in mass ratio weighing are dissolved in the methanol and deionized water mixed solution of arbitrary proportion,
It is configured to solution A, wherein 0.5≤x≤10；The potassium ferricyanide is dissolved in deionized water, is configured to the solution that concentration is 0.04mol/L
B；Solution B is poured into solution A, is uniformly mixed, acquisition solution C, 6-24 hours static at room temperature, separating-purifying and drying,
It can be obtained target product.
Target product microscopic appearance is the micron or sub-micron hollow cube of favorable dispersibility, and changing technical parameter can shadow
Microscopic dimensions and degree of hollowness are rung, appearance structure will not be had an impact.
Increase the mass ratio of manganese source and chelating agent, i.e. raising manganese ion concentration, subtracts material crystalline decrease, microcosmic partial size
Small, cube wall thickness reduces.
The process needs that solution A is added in solution B are poured into rapidly, and static mixing naturally.
The preferred anhydrous Manganese chloride of manganese source, the preferred trisodium citrate dihydrate of chelating agent.
Shorten solution C quiescent time, weakens material crystalline, microcosmic partial size reduces, cube wall thickness reduces.
Separating-purifying mode is centrifugation, is washed 2-3 times repeatedly using deionized water and ethyl alcohol；Drying mode is 60 DEG C of bakings
It is dry.
Application method of the manganese systems Prussian blue analogue material for lithium ion battery negative material is:
(1) manganese systems Prussian blue analogue material, acetylene black and sodium carboxymethylcellulose (cmc) are weighed；Its mass ratio is X:(9-
X): mixed material is transferred in ball grinder by 1,6≤X≤8, and appropriate amount of deionized water is added, makes mixture pulp, and ball milling 6~
10 hours, the slurry after ball milling is uniformly coated on copper foil；Electrode slice after film is dry 12~24 at 55~120 DEG C
It after hour, is suppressed with roll squeezer to enhance the adhesiveness of electrode material consistency and material and collector, cuts and electricity is made
Pole piece；
It (2) is to electrode with lithium metal in argon atmosphere, polyethylene porous membrane is diaphragm, electrolyte is 0.5~
The lithium hexafluoro phosphate of 1.0mol/L is dissolved in ethylene carbonate (EC): methyl ethyl carbonate (EMC): diethyl carbonate (DEC) is by body
Product is than being assembled into button cell in 1:1:1 mixed solution.
Button type battery carries out constant current charge-discharge capacity and cycle performance test, test result:
Manganese systems Prussian blue analogue material is under the current density of 100mA/g, and specific discharge capacity is by microcosmic partial size and degree of hollowness
It influences less, it is final to stablize in 700mAh/g or more；When being sequentially increased current density to 200,500,1000,2000,5000mA/
G, the material that microcosmic partial size is small and degree of hollowness is big have a more excellent chemical property, specific discharge capacity is respectively 490,
430,400,320,210mAh/g；When electric current restores to 100mA/g, capacity still is able to restore to 700mAh/g, is filled
Divide and shows high specific capacity and excellent high rate performance.
The utility model has the advantages that as the above scheme is adopted, hollow manganese systems Prussian blue analogue material is obtained by one-step synthesis,
By reactant concentration, reaction time technical parameter in regulation reaction process, to a step of Prussian blue analogue material microscopic appearance
Control synthesis, the microcosmic partial size and degree of hollowness of stability contorting material obtain the manganese systems of a series of diverse microcosmic sizes and degree of hollowness
Prussian blue analogue material promotes material electrochemical performance, and the partial size and degree of hollowness of product are highly controllable, and synthetic route is raw materials used
It is easy to get, realizes the synthesis quick, cheap to manganese systems Prussian blue analogue material, method is easy, and products therefrom is high-purity, partial size
It is evenly distributed, the quasi- monocrystalline body of cube pattern, is easy to large-scale industrial production, reduces production cost to a certain degree, it will
Negative electrode material of the manganese systems Prussian blue analogue material as lithium ion battery enhances the popularity of such material application.Wherein, needle
The case where to low operating current, can reduce reactant concentration, to reduce production cost, with the increase of operating current, Ke Yishi
When reducing the reaction time, increasing reactant concentration, the manganese systems Prussian blue analogue material that microcosmic partial size is small, degree of hollowness is big is synthesized, with
Utilize its more excellent high rate performance.
Advantage: this method synthetic route is simple, and raw material is easy to get, convenient for regulation, it is easy to accomplish macroblock quantization preparation, by the material
Show excellent circulation and high rate performance as negative electrode of lithium ion battery, this technique operating current according to needed for device it is big
Small regulation response parameter, to synthesize scantling specification the most applicable.
Detailed description of the invention
Fig. 1 is that the powder X-ray of manganese systems Prussian blue analogue material under differential responses object concentration conditions of the invention spreads out
Penetrate style figure.
Fig. 2 (a) is MnCl of the invention2The SEM image of sample when concentration is 0.02mol/L.
Fig. 2 (b) is MnCl of the invention2Sample TEM image when concentration is 0.02mol/L.
Fig. 2 (c) is MnCl of the invention2The SEM image of sample when concentration is 0.01mol/L.
Fig. 2 (d) is MnCl of the invention2The TEM image of sample when concentration is 0.01mol/L.
Fig. 2 (e) is MnCl of the invention2Sample SEM image when concentration is 0.005mol/L.
Fig. 2 (f) is MnCl of the invention2The TEM image of sample when concentration is 0.005mol/L.
Fig. 3 is the embodiment of the present invention 1, and the sample for manganese systems Prussian blue analogue material under differential responses object concentration conditions exists
100mA h g-1Simple charge and discharge cycles curve graph.
Fig. 4 is the embodiment of the present invention 1, is the sample of manganese systems Prussian blue analogue material under differential responses object concentration conditions not
With the high rate performance test chart under current density.
Specific embodiment
The present invention is that a kind of control of manganese systems Prussian blue analogue material synthesizes and be used as lithium ion battery negative material,
It takes one-step synthesis to be prepared a nanometer manganese systems Prussian blue analogue material, regulates and controls technical parameter in reaction process, realize to receiving
The accurate control of rice manganese systems Prussian blue analogue material microscopic dimensions and degree of hollowness, and negative electrode of lithium ion battery material is done into its application
Material；
Manganese systems Prussian blue analogue control of material synthesis, comprising the following steps:
Manganese source is selected from anhydrous Manganese chloride (MnCl2) or a chloride hydrate manganese (MnCl2·H2O)；
Source of iron and cyanogen root are selected from the potassium ferricyanide (K3[Fe(CN)6])；
Chelating agent selects anhydrous citric acid sodium or trisodium citrate dihydrate；
Manganese source and chelating agent x:1 in mass ratio weighing are dissolved in the methanol and deionized water mixed solution of arbitrary proportion,
It is configured to solution A, wherein 0.5≤x≤10；The potassium ferricyanide is dissolved in deionized water, is configured to the solution that concentration is 0.04mol/L
B；Solution B is poured into solution A, is uniformly mixed, acquisition solution C, 6-24 hours static at room temperature, separating-purifying and drying,
It can be obtained target product.
Target product microscopic appearance is the micron or sub-micron hollow cube of favorable dispersibility, and changing technical parameter can shadow
Microscopic dimensions and degree of hollowness are rung, appearance structure will not be had an impact.
Increase the mass ratio of manganese source and chelating agent, i.e. raising manganese ion concentration, subtracts material crystalline decrease, microcosmic partial size
Small, cube wall thickness reduces.
The process needs that solution A is added in solution B are poured into rapidly, and static mixing naturally.
The preferred anhydrous Manganese chloride of manganese source, the preferred trisodium citrate dihydrate of chelating agent.
Shorten solution C quiescent time, weakens material crystalline, microcosmic partial size reduces, cube wall thickness reduces.
Separating-purifying mode is centrifugation, is washed 2-3 times repeatedly using deionized water and ethyl alcohol；Drying mode is 60 DEG C of bakings
It is dry.
Application method of the manganese systems Prussian blue analogue material for lithium ion battery negative material is:
(1) manganese systems Prussian blue analogue material, acetylene black and sodium carboxymethylcellulose (cmc) are weighed；Its mass ratio is X:(9-
X): mixed material is transferred in ball grinder by 1,6≤X≤8, and appropriate amount of deionized water is added, makes mixture pulp, and ball milling 6~
10 hours, the slurry after ball milling is uniformly coated on copper foil；Electrode slice after film is dry 12~24 at 55~120 DEG C
It after hour, is suppressed with roll squeezer to enhance the adhesiveness of electrode material consistency and material and collector, cuts and electricity is made
Pole piece；
It (2) is to electrode with lithium metal in argon atmosphere, polyethylene porous membrane is diaphragm, electrolyte is 0.5~
The lithium hexafluoro phosphate of 1.0mol/L is dissolved in ethylene carbonate (EC): methyl ethyl carbonate (EMC): diethyl carbonate (DEC) is by body
Product is than being assembled into button cell in 1:1:1 mixed solution.
Button type battery carries out constant current charge-discharge capacity and cycle performance test, test result:
Manganese systems Prussian blue analogue material is under the current density of 100mA/g, and specific discharge capacity is by microcosmic partial size and degree of hollowness
It influences less, it is final to stablize in 700mAh/g or more；When being sequentially increased current density to 200,500,1000,2000,5000mA/
G, the material that microcosmic partial size is small and degree of hollowness is big have a more excellent chemical property, specific discharge capacity is respectively 490,
430,400,320,210mAh/g；When electric current restores to 100mA/g, capacity still is able to restore to 700mAh/g, is filled
Divide and shows high specific capacity and excellent high rate performance.
Embodiment 1: the preparation method and structural characterization of lithium ion battery manganese systems Prussian blue analogue material
Manganese source is anhydrous Manganese chloride (MnCl2), iron cyanogen root is from the potassium ferricyanide (K3[Fe(CN)6]), chelate selection two
Citric acid monohydrate sodium；
Weigh three parts of 1mmol anhydrous Manganese chloride (MnCl2) and 2mmol trisodium citrate dihydrate be dissolved completely in respectively
In 25ml, 50ml, 100ml deionized water, achromaticity and clarification clear solution A, solution B and solution C are obtained respectively.Separately weigh 1mmol
The potassium ferricyanide (K3[Fe(CN)6]) be dissolved in 25ml deionized water and obtain solution D, it is agitated be completely dissolved after, by C parts of solution Ds point
It does not pour into solution A, solution B and solution C, obtains solution E, solution F and solution G respectively, after the static 12h of room temperature, centrifugation is received
Collection, is washed 2-3 times repeatedly using deionized water and ethyl alcohol, finally after 60 DEG C dry 12~24 hours, is obtained a series of final
White powder product.
Product is through Bruker D8ADVANCE x-ray powder diffraction instrument with Cu K alpha ray (wavelengthIt sweeps
Retouching leg speed is 0.08 °/sec) identify that product is manganese systems Prussian blue analogue K under differential responses object concentration conditions2Mn[Fe(CN)6]·
2H2O (Fig. 1) matches with JCPDS card standard value No.97-1697, and no other impurity peaks occur, and crystallinity is with reactant concentration
Raising and slightly reduce.Fig. 1 is the powder X-ray of manganese systems Prussian blue analogue material under differential responses object concentration conditions
Diffraction pattern；Wherein left ordinate is relative intensity (Intensity), and abscissa is angle of diffraction (2 θ)；Wherein, in Fig. 1
It (a) is MnCl2The XRD diffraction pattern figure of sample when concentration is 0.02mol/L；(b) in Fig. 1 is MnCl2Concentration is 0.01mol/
The XRD diffraction pattern figure of sample when L；(c) in Fig. 1 is MnCl2The XRD diffraction pattern of sample when concentration is 0.005mol/L
Figure.
Using the pattern of SU8200 field emission scanning electron microscope (voltage 5kV) observation manganese systems Prussian blue analogue material, such as Fig. 2 institute
Show.
Fig. 2 is the SEM image and TEM image of manganese systems Prussian blue analogue material under differential responses object concentration conditions；Wherein, scheme
(a) in 2 is MnCl2The SEM image of sample when concentration is 0.02mol/L；(b) in Fig. 2 is MnCl2Concentration is 0.02mol/L
When sample TEM image；(c) in Fig. 2 is MnCl2The SEM image of sample when concentration is 0.01mol/L；(d) in Fig. 2 is
MnCl2The TEM image of sample when concentration is 0.01mol/L；(e) in Fig. 2 is MnCl2Sample SEM when concentration is 0.005mol/L
Image；(f) in Fig. 2 is MnCl2The TEM image of sample when concentration is 0.005mol/L；Manganese systems Prussian blue analogue scantling
It is evenly distributed, pattern is cube, and soilless sticking phenomenon occurs, and with the raising of reactant concentration, microcosmic partial size reduces, and wall thickness subtracts
Small, degree of hollowness increases.
Electrochemical property test: by weight for 6:3:1 ratio claim respectively manganese systems Prussian blue analogue material, acetylene black and
Sodium carboxymethylcellulose (cmc)；Mixed material is transferred in ball grinder, appropriate amount of deionized water is added, makes mixture at paste
Shape ball milling 6 hours, the slurry after ball milling is uniformly coated on copper foil；It is small that electrode slice after film dries 12 at 55 DEG C
Shi Hou, suppressed with roll squeezer with enhance the consistency of electrode material and with the adhesiveness of collector, cut obtained electrode slice,
Finally in vacuum drying oven 120 DEG C of dry 12h move back it is spare in glove box；In the glove box environment full of argon gas, with gold
Belonging to lithium is to electrode, and polyethylene porous membrane is diaphragm, and electrolyte is that the lithium hexafluoro phosphate of 0.5~1.0mol/L is dissolved in carbonic acid second
Enester (EC): methyl ethyl carbonate (EMC): diethyl carbonate (DEC) in 1:1:1 mixed solution, is assembled into button electricity by volume
Pond simultaneously carries out constant current charge-discharge capacity and high rate performance test, and chemical property is as shown in Figure 3 and Figure 4.
Fig. 3 is the sample of manganese systems Prussian blue analogue material under differential responses object concentration conditions in 100mA h g-1Simply fill
Discharge cycles curve graph；Wherein, (a) in Fig. 3 is MnCl2Sample is in 100mA h g when concentration is 0.02mol/L-1It is simple
Charge and discharge cycles curve graph；(b) in Fig. 3 is MnCl2Sample is in 100mA h g when concentration is 0.01mol/L-1Simple charge and discharge
Electric cyclic curve figure；(c) in Fig. 3 is MnCl2Sample is in 100mA h g when concentration is 0.005mol/L-1Simple charge and discharge
Cyclic curve figure.
Fig. 4 is times of the sample of manganese systems Prussian blue analogue material under differential responses object concentration conditions under different current densities
Rate performance test chart；(a) in Fig. 4 is MnCl2High rate performance of the sample under different current densities when concentration is 0.02mol/L
Test chart；(b) in Fig. 4 is MnCl2High rate performance test of the sample under different current densities when concentration is 0.01mol/L
Figure；(c) in Fig. 4 is MnCl2High rate performance test chart of the sample under different current densities when concentration is 0.005mol/L.
Embodiment 2: 1mmol anhydrous Manganese chloride (MnCl is weighed2), 2mmol trisodium citrate dihydrate is dissolved completely in 25ml
In deionized water, achromaticity and clarification clear solution A is obtained.The 1mmol potassium ferricyanide (K is weighed again3[Fe(CN)6]) be dissolved in 25ml go from
Solution B is obtained in sub- water, solution B is poured into solution A and is uniformly mixed, solution C is obtained, stands 6h respectively at room temperature, separation mentions
It is pure, after 60 DEG C dry 12~24 hours, obtain white powder product.Product is manganese systems Prussian blue analogue, and microscopic appearance is vertical
Cube, microcosmic partial size are 150~180nm.
Embodiment 3: mono- chloride hydrate manganese (MnCl of 0.5mmol is weighed2·H2O), 2mmol anhydrous citric acid sodium is completely dissolved
In 25ml deionized water, achromaticity and clarification clear solution A is obtained.The 1mmol potassium ferricyanide (K is weighed again3[Fe(CN)6]) be dissolved in
Obtain solution B in 25ml deionized water, solution B poured into after solution A and is uniformly mixed, solution C is obtained, at room temperature it is static for 24 hours,
Obtain final white powdered product.Product is manganese systems Prussian blue analogue, and microscopic appearance is cube, particle diameter distribution 310~
410nm。
Claims (7)
1. a kind of lithium ion battery synthetic method of manganese systems Prussian blue analogue material, it is characterized in that: taking one-step synthesis legal system
It is standby to obtain manganese systems Prussian blue analogue material, regulate and control technical parameter in reaction process, realizes to manganese systems Prussian blue analogue material
The accuracy controlling of particle size and degree of hollowness, and lithium ion battery negative material is done into its application；
Manganese systems Prussian blue analogue control of material synthesis, comprising the following steps:
Manganese source is selected from anhydrous Manganese chloride (MnCl2) or a chloride hydrate manganese (MnCl2·H2O)；
Source of iron and cyanogen root are selected from the potassium ferricyanide (K3[Fe(CN)6])；
Chelating agent selects anhydrous citric acid sodium or trisodium citrate dihydrate；
Manganese source and chelating agent x:1 in mass ratio weighing are dissolved in the methanol and deionized water mixed solution of arbitrary proportion, prepared
At solution A, wherein 0.5≤x≤10；The potassium ferricyanide is dissolved in deionized water, is configured to the solution B that concentration is 0.04mol/L；It will
Solution B is poured into solution A, is uniformly mixed, and solution C, 6-24 hours static at room temperature, separating-purifying and drying are obtained
Obtain target product.
2. a kind of synthetic method of the lithium ion battery according to claim 1 with manganese systems Prussian blue analogue material, feature
It is: increases the mass ratio of manganese source and chelating agent, is i.e. raising manganese ion concentration, weakens material crystalline, microcosmic partial size reduces, vertical
Cube wall thickness reduces.
3. a kind of synthetic method of the lithium ion battery according to claim 1 with manganese systems Prussian blue analogue material, feature
It is: the process needs that solution A is added in solution B is poured into rapidly, and static mixing naturally.
4. a kind of synthetic method of the lithium ion battery according to claim 1 with manganese systems Prussian blue analogue material, feature
It is: the preferred anhydrous Manganese chloride of manganese source, the preferred trisodium citrate dihydrate of chelating agent.
5. a kind of synthetic method of the lithium ion battery according to claim 1 with manganese systems Prussian blue analogue material, feature
It is: shortens solution C quiescent time, weakens material crystalline, microcosmic partial size reduces, cube wall thickness reduces.
6. a kind of synthetic method of the lithium ion battery according to claim 1 with manganese systems Prussian blue analogue material, feature
Be: separating-purifying mode is centrifugation, is washed 2-3 times repeatedly using deionized water and ethyl alcohol；Drying mode is 60 DEG C of drying.
7. it is a kind of using the claim 1 lithium ion battery application method of manganese systems Prussian blue analogue material, it is characterized in that: manganese systems
Application method of the Prussian blue analogue material for lithium ion battery negative material is:
(1) manganese systems Prussian blue analogue material, acetylene black and sodium carboxymethylcellulose are weighed；Its mass ratio is X:(9-X): 1,6≤X
≤ 8, mixed material is transferred in ball grinder, appropriate amount of deionized water is added, makes mixture pulp, it ball milling 6~10 hours, will
Slurry after ball milling is uniformly coated on copper foil；Electrode slice after film after drying 12~24 hours, is used at 55~120 DEG C
Roll squeezer is suppressed to enhance the adhesiveness of electrode material consistency and material and collector, and obtained electrode slice is cut；
It (2) is to electrode with lithium metal in argon atmosphere, polyethylene porous membrane is diaphragm, and electrolyte is 0.5~1.0mol/L
Lithium hexafluoro phosphate be dissolved in ethylene carbonate: methyl ethyl carbonate: diethyl carbonate is by volume in 1:1:1 mixed solution, group
Dress up button cell.
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| CN114256460A (en) * | 2022-01-08 | 2022-03-29 | 温州大学碳中和技术创新研究院 | Large-scale preparation of high-crystallization Prussian blue analogue for sodium ion battery by 'water-in-salt' microreactor principle |
| CN114873610A (en) * | 2022-04-28 | 2022-08-09 | 东北大学秦皇岛分校 | Preparation method of hollow cobalt system Prussian blue electrode material |
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| CN113145040A (en) * | 2021-05-31 | 2021-07-23 | 青岛科技大学 | Method for preparing Prussian blue analogue by micro-channel reactor |
| CN114256460A (en) * | 2022-01-08 | 2022-03-29 | 温州大学碳中和技术创新研究院 | Large-scale preparation of high-crystallization Prussian blue analogue for sodium ion battery by 'water-in-salt' microreactor principle |
| CN114256460B (en) * | 2022-01-08 | 2023-07-07 | 温州大学碳中和技术创新研究院 | Large-scale preparation of high-crystallization Prussian blue analogues for sodium ion battery by using salt water-in-water microreactor principle |
| CN114873610A (en) * | 2022-04-28 | 2022-08-09 | 东北大学秦皇岛分校 | Preparation method of hollow cobalt system Prussian blue electrode material |
| CN114873610B (en) * | 2022-04-28 | 2023-12-12 | 东北大学秦皇岛分校 | Preparation method of hollow cobalt Prussian blue electrode material |
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