CN109755490A - A kind of Prussian blue electrode material and its preparation and application - Google Patents
A kind of Prussian blue electrode material and its preparation and application Download PDFInfo
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- CN109755490A CN109755490A CN201711090633.6A CN201711090633A CN109755490A CN 109755490 A CN109755490 A CN 109755490A CN 201711090633 A CN201711090633 A CN 201711090633A CN 109755490 A CN109755490 A CN 109755490A
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- prussian blue
- iron
- electrode material
- nickel
- potassium ferricyanide
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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 relates to a kind of Prussian blue electrode material and its preparation and application.The present invention coats one layer of fine and close iron cyaniding nano nickel particles in Prussian blue electrode material surface by two step coprecipitations, and is used as water system kalium ion battery positive electrode.Iron nickel cyanide protective layer structure is stablized, and ionic conductivity is good, and has good electrochemical reversibility, and when the Prussian blue electrode material of iron cyaniding nickel coated is used as water system kalium ion battery anode, forthright again and electrochemical stability is significantly improved.In addition, the Prussian blue electrode material of iron cyaniding nickel coated also has safety and environmental protection, cheap advantage all has wide application prospect in high-performance power battery and electrochemical energy storage cell technology.
Description
Technical field:
The present invention relates to Study on Li-ion batteries field, in particular to a kind of Prussian blue electrode material and its preparation and answer
With.
Technical background:
Extensive energy storage technology is the key that realize that renewable energy efficiently utilizes.Water-system alkali metal ion battery has height
It the advantages that safety, low cost, high power density, is widely paid close attention to by researchers.Wherein study earliest be water system lithium from
Sub- battery, however limited by lithium source reserves, the cost advantage of aquo-lithium ion battery does not protrude.And reserves of the potassium in the earth's crust
Much higher than lithium (content of the potassium in the earth's crust be 2.47%, and lithium be only 0.0065%), and lithium ion in the solution migration speed
Degree is fast, therefore water system kalium ion battery has broader practice prospect.However, the biggish ionic radius of potassium ion and high ionization
Potential keeps its optional electrode material limited.It is Prussian blue that there is perovskite structure, three-dimensional network skeleton, big gap site
Be conducive to the quick deintercalation of potassium ion.Therefore, Prussian blue and the like is more appropriate kalium ion battery positive electrode.
But the presence of fault of construction and Interstitial Water that Prussian blue material generates in the synthesis process has seriously affected its stable structure
Property.And iron nickel cyanide belongs to Prussian blue similar object, has similar structure with Prussian blue, is not likely to produce knot in synthesis process
Structure defect, crystallinity are high, and structural stability is good, but its theoretical discharge specific capacity only 70mA h/g, far below Prussian blue
(170mA h/g)。
Summary of the invention:
In order to solve the above technical problems, the present invention coats one layer of cause in Prussian blue electrode material surface by coprecipitation
Close iron cyaniding nano nickel particles, and it is used as water system kalium ion battery positive electrode.
In order to achieve the above objectives, the specific technical solution that the present invention uses is as follows:
Prussian blue electrode material of the electrode material for iron cyaniding nickel coated, structural formula FeHCF-NiHCF, wherein
FeHCF is Prussian, and NiHCF is iron cyaniding nickel compound, wherein the mass content 10wt.%- of iron nickel cyanide
50wt.%.
(1) potassium ferricyanide and iron chloride are dissolved separately in deionized water, the concentration of the potassium ferricyanide is 0.01~1M, iron
The concentration of potassium cyanide and iron chloride ratio is 1:(1+x), x=0.5~2.5.Potassium ferricyanide solution is slowly dropped to same volume
Ferric chloride solution in, after 40~80 DEG C are stirred to react 2~8h, be centrifugated out sediment, and repeatedly clear with deionized water
It washes, Prussian blue particle (FeHCF) is made in grinding after 60~100 DEG C of vacuum drying.
(2) it disperses above-mentioned Prussian blue particle in the deionized water of certain volume, granule density is 5~50mg/mL.
The potassium ferricyanide and nickel chloride are dissolved separately in deionized water, the amount of the substance of the potassium ferricyanide is that preparation is Prussian blue corresponding
The concentration ratio of the 1/20~1/2 of the amount of potassium ferricyanide substance used when grain, the potassium ferricyanide and nickel chloride is 1:(1+x), x=0.5
~2.5.Isometric potassium ferricyanide solution and nickel chloride solution are slowly added drop-wise in Prussian blue dispersion liquid simultaneously, 40~
After 80 DEG C are stirred to react 2~8h, it is centrifugated out sediment, and be cleaned multiple times with deionized water, after 60~100 DEG C of vacuum drying
Grind the Prussian blue particle (FeHCF-NiHCF) that iron cyaniding nickel coated is made.
(3) electrode material and conductive agent, binder are prepared by mixing into electrode as water system kalium ion battery anode.
(4) electrodes conduct agent made from step (3) can be one kind of Super P, acetylene black, carbon nanotube, graphene etc.
Or it is several；Binder can be the one or more of PVDF, PTFE, CMC+SBR etc.；Collector used can be aluminium foil, copper foil, stainless
The one or more of steel mesh, nickel foil, titanium foil etc.；The cell electrolyte is K2SO4,KNO3,CH3COOK,KF6,LiTFSI,
LiClO4,KOH,KCl,KH2PO4,KBr,K2CO3One or more.The solvent of the battery electrolyte is water, the matter of electrolyte
Measure concentration 0.1M-20M.
Beneficial effect
Iron nickel cyanide protective layer structure is stablized, and ionic conductivity is good, and has good electrochemical reversibility, modified general
When Shandong scholar's indigo plant electrode material is used as water system kalium ion battery anode, forthright again and electrochemical stability is significantly improved.The present invention
The high iron nickel cyanide of stability is coated by coprecipitation on Prussian blue surface obtained, and is used as water system potassium ion electricity
Pond positive electrode, the structural stability and electrochemical stability of modified Prussian blue electrode material significantly improve.In addition, general
Shandong scholar is blue and its modified material also has safety and environmental protection, cheap advantage, in high-performance power battery and electrochemical energy storage
Wide application prospect is all had in battery technology.In preparation method, this method of modifying is simple, easy to operate, at low cost, and
Effect is obvious, has industrial prospect.
Detailed description of the invention
Fig. 1: Prussian blue and its modified material is used as high rate performance when water system kalium ion battery anode；
Fig. 2: Prussian blue and its modified material is used as cycle performance when water system kalium ion battery anode.
Specific embodiment
Experimental example:
(1) the 0.1M potassium ferricyanide and 0.2M iron chloride are dissolved separately in 100mL deionized water.By potassium ferricyanide solution
It is slowly dropped in ferric chloride solution, after 60 DEG C are stirred to react 6h, is centrifugated out sediment, and repeatedly clear with deionized water
It washes, Prussian blue particle (FeHCF) is made in grinding after 70 DEG C of vacuum drying.
(2) it disperses above-mentioned Prussian blue particle in 100mL deionized water, granule density 20mg/mL.By iron cyaniding
Potassium and nickel chloride are dissolved separately in 100mL deionized water, and the concentration of the potassium ferricyanide and nickel chloride is respectively 0.01M and 0.02M.
Potassium ferricyanide solution and nickel chloride solution are slowly added drop-wise in Prussian blue dispersion liquid simultaneously, after 60 DEG C are stirred to react 6h,
It is centrifugated out sediment, and is cleaned multiple times with deionized water, is ground after 70 DEG C of vacuum drying and the general of iron cyaniding nickel coated is made
Shandong scholar's indigo plant particle (FeHCF-NiHCF).
(3) electrode material and conductive agent, binder are prepared by mixing into electrode as water system kalium ion battery anode.Activity
Substance: Super P (conductive agent): PTFE (binder)=7:2:1 (mass ratio) is done using activated carbon electrodes to electrode, saturation
Calomel electrode is reference electrode, 0.5M K2SO4Solution is electrolyte, has carried out electro-chemical test to the Prussian blue electrode of modification.
Comparative example:
(1) the 0.1M potassium ferricyanide and 0.2M iron chloride are dissolved separately in 100mL deionized water.By potassium ferricyanide solution
It is slowly dropped in ferric chloride solution, after 60 DEG C are stirred to react 6h, is centrifugated out sediment, and repeatedly clear with deionized water
It washes, Prussian blue particle (FeHCF) is made in grinding after 70 DEG C of vacuum drying.
(2) electrode material and conductive agent, binder are prepared by mixing into electrode as water system kalium ion battery anode.Activity
Substance: Super P (conductive agent): PTFE (binder)=7:2:1 (mass ratio) is done using activated carbon electrodes to electrode, saturation
Calomel electrode is reference electrode, 0.5M K2SO4Solution is electrolyte, has carried out electro-chemical test to the Prussian blue electrode of modification.
It can be seen that by Fig. 1, iron nickel cyanide ionic conductivity is good, and modified high rate performance significantly improves.It can from Fig. 2
Out, iron nickel cyanide protective layer structure is stablized, and modified cycle performance significantly improves.
Claims (5)
1. a kind of Prussian blue electrode material, it is characterised in that: the electrode material is the Prussian blue electricity of iron cyaniding nickel coated
Pole material, structural formula FeHCF-NiHCF, wherein FeHCF is Prussian, and NiHCF is iron cyaniding nickel compound,
The mass content 10wt.%-50wt.% of middle iron nickel cyanide.
2. the preparation method of Prussian blue electrode material described in a kind of claim 1, it is characterised in that: preparation process is as follows:
(1) potassium ferricyanide and iron chloride are dissolved separately in deionized water, the concentration of the potassium ferricyanide is 0.01~1M, iron cyaniding
The concentration of potassium and iron chloride ratio is 1:(1+x), x=0.5~2.5；Potassium ferricyanide solution is added drop-wise to the iron chloride of same volume
In solution, after 40~80 DEG C are stirred to react 2~8h, it is centrifugated out sediment, and cleaned with deionized water, 60~100 DEG C
Prussian blue particle FeHCF is made in grinding after vacuum drying；
(2) it disperses above-mentioned Prussian blue particle in deionized water, granule density is 5~50mg/mL；By the potassium ferricyanide and chlorine
Change nickel to be dissolved separately in deionized water, the amount of the substance of the potassium ferricyanide is iron cyaniding used when preparing corresponding Prussian blue particle
The concentration ratio of the 1/20~1/2 of the amount of potassium substance, the potassium ferricyanide and nickel chloride is 1:(1+x), x=0.5~2.5；It will be isometric
Potassium ferricyanide solution and nickel chloride solution slowly simultaneously be added drop-wise in Prussian blue dispersion liquid, be stirred to react 2 at 40~80 DEG C
After~8h, it is centrifugated out sediment, and cleaned with deionized water, is ground after 60~100 DEG C of vacuum drying and iron nickel cyanide is made
The Prussian blue electrode material FeHCF-NiHCF of cladding.
3. a kind of application of material described in claim 1, it is characterised in that: the Prussian blue electrode material of the iron cyaniding nickel coated
Material is used as water system kalium ion battery positive electrode active materials.
4. the application of material as claimed in claim 3, it is characterised in that: the electrolyte in the water system kalium ion battery electrolyte
It can be K2SO4,KNO3,CH3COOK,KF6,LiTFSI,LiClO4,KOH,KCl,KH2PO4,KBr,K2CO3One kind or two kinds with
On.
5. the application of material as claimed in claim 3, it is characterised in that: the electrolyte solvent is aqueous solvent, the matter of electrolyte
Measure concentration 0.1M-20M.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711090633.6A CN109755490B (en) | 2017-11-08 | 2017-11-08 | Prussian blue electrode material and preparation and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711090633.6A CN109755490B (en) | 2017-11-08 | 2017-11-08 | Prussian blue electrode material and preparation and application thereof |
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| CN109755490A true CN109755490A (en) | 2019-05-14 |
| CN109755490B CN109755490B (en) | 2022-01-28 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110391407A (en) * | 2019-07-15 | 2019-10-29 | 广东邦普循环科技有限公司 | A kind of power battery anode material of core-shell structure and its preparation method and application |
| CN115745030A (en) * | 2023-01-09 | 2023-03-07 | 浙江帕瓦新能源股份有限公司 | Positive electrode material of potassium ion battery, precursor of positive electrode material and preparation method of positive electrode material |
Citations (4)
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| CN105098157A (en) * | 2015-07-24 | 2015-11-25 | 北京理工大学 | Preparation method of Fe4[Fe(CN)6]3@Co3[Co(CN)6]2 composite material and application of Fe4[Fe(CN)6]3@Co3[Co(CN)6]2 composite material |
| KR20170036881A (en) * | 2015-09-18 | 2017-04-03 | 건국대학교 글로컬산학협력단 | Method for manufacturin bimetallic prussian blue analogue with cyanometallate |
| CN106910888A (en) * | 2017-01-14 | 2017-06-30 | 复旦大学 | A kind of potassium/Prussian blue secondary cell |
| CN107240714A (en) * | 2017-06-29 | 2017-10-10 | 厦门大学 | One kind can discharge and recharge aluminium ion battery and preparation method thereof |
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2017
- 2017-11-08 CN CN201711090633.6A patent/CN109755490B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105098157A (en) * | 2015-07-24 | 2015-11-25 | 北京理工大学 | Preparation method of Fe4[Fe(CN)6]3@Co3[Co(CN)6]2 composite material and application of Fe4[Fe(CN)6]3@Co3[Co(CN)6]2 composite material |
| KR20170036881A (en) * | 2015-09-18 | 2017-04-03 | 건국대학교 글로컬산학협력단 | Method for manufacturin bimetallic prussian blue analogue with cyanometallate |
| CN106910888A (en) * | 2017-01-14 | 2017-06-30 | 复旦大学 | A kind of potassium/Prussian blue secondary cell |
| CN107240714A (en) * | 2017-06-29 | 2017-10-10 | 厦门大学 | One kind can discharge and recharge aluminium ion battery and preparation method thereof |
Non-Patent Citations (2)
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| MIN WAN ET AL.: "Core-shell hexacyanoferrate for superior Na-ion batteries", 《JOURNAL OF POWER SOURCES》 * |
| PRASANNA ET AL.: "Prussian Green: A High Rate Capacity Cathode for Potassium Ion Batteries", 《ELECTROCHIMICA ACTA》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110391407A (en) * | 2019-07-15 | 2019-10-29 | 广东邦普循环科技有限公司 | A kind of power battery anode material of core-shell structure and its preparation method and application |
| CN115745030A (en) * | 2023-01-09 | 2023-03-07 | 浙江帕瓦新能源股份有限公司 | Positive electrode material of potassium ion battery, precursor of positive electrode material and preparation method of positive electrode material |
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| Publication number | Publication date |
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| CN109755490B (en) | 2022-01-28 |
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