CN108390026A - A kind of cage positive electrode and its preparation method and application - Google Patents
A kind of cage positive electrode and its preparation method and application Download PDFInfo
- Publication number
- CN108390026A CN108390026A CN201810058259.XA CN201810058259A CN108390026A CN 108390026 A CN108390026 A CN 108390026A CN 201810058259 A CN201810058259 A CN 201810058259A CN 108390026 A CN108390026 A CN 108390026A
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- China
- Prior art keywords
- positive electrode
- cage
- anode
- cage positive
- perchlorate
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Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 19
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 239000010405 anode material Substances 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000011572 manganese Substances 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 150000004673 fluoride salts Chemical class 0.000 claims description 8
- CKFMJXZQTNRXGX-UHFFFAOYSA-L iron(2+);diperchlorate Chemical compound [Fe+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O CKFMJXZQTNRXGX-UHFFFAOYSA-L 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- QVRFMRZEAVHYMX-UHFFFAOYSA-L manganese(2+);diperchlorate Chemical compound [Mn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O QVRFMRZEAVHYMX-UHFFFAOYSA-L 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000006245 Carbon black Super-P Substances 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N NMP Substances CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 239000005030 aluminium foil Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 5
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 3
- -1 hexafluorophosphate Chemical compound 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims 2
- 238000004321 preservation Methods 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 239000007772 electrode material Substances 0.000 abstract description 4
- 239000011734 sodium Substances 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 239000011698 potassium fluoride Substances 0.000 description 4
- 239000011775 sodium fluoride Substances 0.000 description 4
- 235000013024 sodium fluoride Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021260 NaFe Inorganic materials 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000001905 inorganic group Chemical group 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021135 KPF6 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 125000001153 fluoro group Chemical class F* 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M4/362—Composites
-
- 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
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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 belongs to electrode material preparing technical fields, and in particular to the chemical formula of a kind of cage positive electrode, the positive electrode is AnM(OH)qX1‑qLm, wherein wherein A is any one in Na, K, Ca, Mg, Al or Zn, and at least one of M Cr, Mn, Fe, Co, Ni or Cu, X F, Cl, Br, CO, CO3、S、SO3Or SO4In any one, L CH3COO、O2CC6H4CO2、C5H5N、(CH3)2Any one in NC (O) H or CN, 0≤n≤2,0<q<1,0<m≤3.The present invention also provides a kind of preparation methods of above-mentioned cage positive electrode.It is used to prepare the anode of metal ion battery the present invention also provides a kind of cage positive electrode and makes battery.The cage positive electrode of the present invention can replace anode material for lithium-ion batteries, have large-sized channel in its skeleton, being capable of the big metal ion of embedding de- size.
Description
Technical field
The invention belongs to electrode material preparing technical fields, and in particular to a kind of cage positive electrode and preparation method thereof and
Using.
Background technology
Battery is a kind of electrochemical appliance that can convert chemical energy and electric energy project.Traditional plumbic acid, ni-mh, ni-Cd
Battery plays important role in energy energy storage field all the time；Lithium ion battery is widely used in mobile phone at present, notes
In the mobile electronic devices such as this computer, also there is increasing market to apply in electric vehicle field.Solar energy, wind energy electricity
It stands and the paddy of cutting of power grid fills out peak, all there is huge demand in the fields such as frequency modulation to energy-storage battery.Poison of the lead-acid battery because of lead
Property and its short service life and low energy density cannot be satisfied the requirement of extensive energy storage.Lithium ion battery uses storage lithium
Compound swaps between positive electrode and negative electrode and realizes the function of energy storage as anode and negative material, lithium battery.It is common
Anode material for lithium-ion batteries include cobalt acid lithium, LiMn2O4, lithium-nickel-manganese-cobalt oxide and LiFePO4, negative material are usual
For graphitic carbon and silicon/carbon composite.But content is low in the natural environment and is unevenly distributed for lithium resource, causes lithium original
The price of material persistently rises.Demand and its mineral deposits to lithium have caused the other types of metal ion battery of manufacture and have made
For the demand of its substitute.
Similar with lithium ion battery, metal ion battery uses metal ion host compound as its electrode material,
Middle metal ion can be reversible in the gap of electrode material movement.Commonly be capable of embedding lithium ionic insertion/deinsertion compound because compared with
Small void size, in the big metal ion such as Na of embedding de- other sizes+、K+、Mg2+、Zn2+、Al3+It is broken etc. structure can be caused
It is bad.Therefore, it is necessary to accommodate these metal ions in metal ion battery using the new material with wide arc gap space.
Invention content
It is an object of the invention to overcome the defect of the prior art, a kind of cage positive electrode, the positive electrode are provided
Anode material for lithium-ion batteries can be replaced, in its skeleton have large-sized channel, can the big metal of embedding de- size from
Son；It is used to prepare metal ion battery the present invention also provides a kind of preparation method of cage positive electrode and by cage positive electrode
Anode and prepare battery.
To achieve the above object, the present invention uses following technical scheme：
The chemical formula of a kind of cage positive electrode, the positive electrode is AnM(OH)qX1-qLm,
Wherein A is any one in Na, K, Ca, Mg, Al or Zn, at least one of M Cr, Mn, Fe, Co, Ni or Cu, X
For F, Cl, Br, CO, CO3、 S、SO3Or SO4In any one, L CH3COO、O2CC6H4CO2、C5H5N、(CH3)2NC(O)H
Or any one in CN, 0≤n≤2,0<q<1,0<m≤3.
Preferably, A is Na or K, and M is one kind in the combination of Fe and Mn, Fe, Mn, X F, Cl or SO4In one kind, L
For O2CC6H4CO2、C5H5One kind in N or CN.
Further, the microstructure of the cage positive electrode is that M forms MO with oxygen6Octahedron, MO6Octahedron passes through altogether
Angle forms parallel chain, chain MO6It is crosslinked by L by forms big channel.
Further, when M is the combination of Fe and Mn, the chemical formula of the positive electrode is
AnFexMn1-x(OH)qX1-qLm, wherein 0<x<1,0≤n≤2,0<q<1,0<m≤3.
Preferably, when X is F, L O2CC6H4CO2When, the chemical formula of the positive electrode is
AnFexMn1-x(OH)qF1-q(O2CC6H4CO2)m, wherein A be Na or K, 0<x<1,0<N≤2,0<q<1,0<m≤3.
The present invention also provides a kind of preparation method of above-mentioned cage positive electrode, the chemical formula of the positive electrode is
AnFexMn1-x(OH)qF1-q(O2CC6H4CO2)m, wherein A be Na or K, 0<x<1,0<N≤2,0<q<1,0<m≤3；This method includes
Following steps：
（1）Perchlorate, ferrous perchlorate, Manganese perchlorate, 1,4- phthalic acids and fluoride salt are dispersed in dimethylformamide
In, stirring；
（2）Polytetrafluoroethyllining lining is transferred to after stirring evenly to obtain in stainless steel cauldron in isothermal holding；
（3）By the product of gained after filtering is washed, vacuum drying obtains final product.
As positive electrode AnFexMn1-x(OH)qF1-q(O2CC6H4CO2)mIn A be Na when, perchlorate NaClO4, fluorine
Salt dissolving is NaF；When A is K, perchlorate KClO4, fluoride salt KF.
Further, step（2）The temperature of middle isothermal holding is 120~150 DEG C, step（3）In vacuum drying temperature
It is 100-150 DEG C.
The present invention also provides a kind of applications of above-mentioned cage positive electrode, which is used to prepare metal ion
Positive electrode, carbon black Super-P, PVDF and NMP are mixed and made into slurry by the anode of battery, are coated on aluminium foil, compacting is cut into
Disk obtains anode.
Further, using the disk as anode, potassium metal is as cathode, and glass fiber filter paper is as diaphragm, hexafluoro phosphorus
The EC/DEC solution of hydrochlorate is electrolyte, dresses up button cell.
Compared with prior art, the invention has the advantages that：
（1）The cage positive electrode of the present invention can replace anode material for lithium-ion batteries, have in its skeleton large-sized
Channel, being capable of the big metal ion of embedding de- size；
（2）Cage positive electrode provided by the invention can be used for preparing the anode of large scale metal ion battery and prepare electricity
Pond.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
Other attached drawings are obtained according to these attached drawings.
Fig. 1 is the micro-structure diagram of cage positive electrode provided in an embodiment of the present invention；
Fig. 2 is the micro-structure diagram of cage positive electrode provided in an embodiment of the present invention；
Fig. 3 is the KFe that the embodiment of the present invention three provides0.5Mn0.5(OH)0.8F0.2(O2CC6H4CO2) prepare battery charge and discharge
Test chart.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clearly and completely
Description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this hair
Embodiment in bright, all other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, shall fall within the protection scope of the present invention.
The embodiment of the present invention provides a kind of cage positive electrode, and the chemical formula of the positive electrode is AnM(OH)qX1-qLm,
Middle A be Na, K, Ca, Mg, Al or Zn in any one, at least one of M Cr, Mn, Fe, Co, Ni or Cu, X F, Cl,
Br、CO、CO3、 S、SO3Or SO4In any one, L CH3COO、O2CC6H4CO2、C5H5N、(CH3)2In NC (O) H or CN
Any one, 0≤n≤2,0<q<1,0<m≤3.The cage positive electrode of the present invention can replace anode material for lithium-ion batteries,
There is large-sized channel in its skeleton, it being capable of the big metal ion of embedding de- size.
Further, the microstructure of the cage positive electrode is that metal M forms MO with oxygen6Octahedron, MO6Octahedron is logical
It crosses corner-sharing and forms parallel chain, chain MO6It is crosslinked by L by forms big channel.
Cage compound proposed by the invention has a variety of space structures by what organic group and inorganic group were constituted
（Including cluster, chain or stratiform）Substance.There is large-sized tunnel or cage structure in its skeleton, can accommodate more
Plant water phase either Examples of non-aqueous solvents molecule or metal hydration or non-hydrated ion.As Figure 1-Figure 2, when inorganic group is
When 3d transition metal, using its empty 3d electron orbit, metal can form stable M-O keys, MO with oxygen6Octahedron passes through altogether
Angle forms parallel chain, these chains MO6Big channel is formed by organic molecule or organic group L crosslinkings；3d simultaneously
Transition metal has a variety of variable valence states, and reversible electronics transfer occurs when other metal ions are embedded in, can do
For ideal metal ion battery material.
Preferably, A is Na or K, and M is one kind in the combination of Fe and Mn, Fe, Mn, X F, Cl or SO4In one kind, L
For O2CC6H4CO2、C5H5One kind in N or CN.
Further, when M is the combination of Fe and Mn, the chemical formula of the positive electrode is
AnFexMn1-x(OH)qX1-qLm, wherein 0<x<1,0≤n≤2,0<q<1,0<m≤3.
Further, when X is F, L O2CC6H4CO2When, the chemical formula of the positive electrode is
AnFexMn1-x(OH)qF1-q(O2CC6H4CO2)m, wherein A be Na or K, 0<x<1,0<N≤2,0<q<1,0<m≤3.
Preferably, the chemical formula of the positive electrode is NaFe0.5Mn0.5(OH)0.8F0.2(O2CC6H4CO2) or KFe0.5Mn0.5
(OH)0.8F0.2(O2CC6H4CO2), wherein A is Na or K, X F, L O2CC6H4CO2, x=0.5, n=1, q=0.8, m=1.
The present invention also provides a kind of preparation method of above-mentioned cage positive electrode, the chemical formula of the positive electrode is
AnFexMn1-x(OH)qF1-q(O2CC6H4CO2)m, wherein A be Na or K, 0<x<1,0<N≤2,0<q<1,0<m≤3；The party
Method includes the following steps：
（1）Perchlorate, ferrous perchlorate, Manganese perchlorate, 1,4- phthalic acids and fluoride salt are dispersed in dimethylformamide
In, stirring；
（2）Polytetrafluoroethyllining lining is transferred to after stirring evenly to obtain in stainless steel cauldron in isothermal holding；
（3）By the product of gained after filtering is washed, vacuum drying obtains final product.
Wherein, as positive electrode AnFexMn1-x(OH)qF1-q(O2CC6H4CO2)mIn A be Na when, perchlorate is
NaClO4, fluoride salt NaF；When A is K, perchlorate KClO4, fluoride salt KF.
Further, step（2）The temperature of middle isothermal holding is 120~150 DEG C, step（3）In vacuum drying temperature
It is 100-150 DEG C.
The present invention also provides a kind of applications of above-mentioned cage positive electrode, which is used to prepare metal ion
Positive electrode, carbon black Super-P, PVDF and NMP are mixed and made into slurry by the anode of battery, are coated on aluminium foil, compacting is cut into
Disk obtains anode.
Further, using the disk as anode, potassium metal is as cathode, and glass fiber filter paper is as diaphragm, hexafluoro phosphorus
The EC/DEC solution of hydrochlorate is electrolyte, dresses up button cell.
Embodiment one
The chemical formula A of the cage positive electrodenM(OH)qX1-qLmIn, when A is Zn, M Ni, X SO4, L CH3COO, n=
When 1.2, q=0.4, m=2, the molecular formula of corresponding positive electrode is Zn1.6Ni(OH)0.4(SO4)0.6(CH3COO)2。
Embodiment two
The chemical formula A of the cage positive electrodenM(OH)qX1-qLmIn, when A is Na, M Fe, X Br, L O2CC6H4CO2, n=
When 1, q=0.7, m=1, the molecular formula of corresponding positive electrode is NaFe (OH)0.7Br0.3(O2CC6H4CO2)。
Embodiment three
When M is the combination of Fe and Mn, the chemical formula of the positive electrode is AnFexMn1-x(OH)qX1-qLm, when A is K, X F, L
For O2CC6H4CO2, x=0.5, n=1, when q=0.8, m=1, the molecular formula of corresponding positive electrode is KFe0.5Mn0.5(OH)0.8F0.2
(O2CC6H4CO2)。
The present embodiment provides cage positive electrode KFe0.5Mn0.5(OH)0.8F0.2(O2CC6H4CO2) preparation method, should
Method includes the following steps：
（1）By potassium hyperchlorate, ferrous perchlorate, Manganese perchlorate, 1,4- phthalic acids and potassium fluoride according to stoichiometric ratio 1~3：
0.5：0.5：1：0.2 is dispersed in dimethylformamide, stirring；The wherein a concentration of 0.05-0.5 of ferrous perchlorate's solution
Mol/L, potassium hyperchlorate, ferrous perchlorate, Manganese perchlorate, Isosorbide-5-Nitrae-phthalic acid and potassium fluoride stoichiometric ratio 1~3：0.5：
0.5：1：0.2.
（2）It is transferred to polytetrafluoroethyllining lining after stirring evenly to obtain in stainless steel cauldron, 1-3 is kept the temperature at 120~150 DEG C
It；
（3）By the product of gained after filtering is washed, it is dried in vacuo 15-30 hours at 100-150 DEG C, obtains final product.
The KFe that will be obtained0.5Mn0.5(OH)0.8F0.2(O2CC6H4CO2) anode of metal ion battery is prepared, step is：
By KFe0.5Mn0.5(OH)0.8F0.2(O2CC6H4CO2), carbon black Super-P, PVDF and NMP be mixed and made into slurry, be coated on aluminium foil
On, 1cm is cut into compacting2Disk；Using the disk as anode, then use potassium metal as cathode, glass fiber filter paper as every
Film, KPF6EC/DEC solution be electrolyte, dress up button cell.Button cell is between 2.5-4.5V in different current ratios
Lower charge-discharge test, if Fig. 3 is that charging and discharging curve, charging process potassium ion are deviate from from positive electrode, seen in 4-4.5V for the first time
Two platforms are observed, the oxidation of ferrous iron and bivalent manganese is corresponded respectively to；Discharge process potassium ion is embedded into positive electrode, point
In 3.7 and 3.5V, there are two discharge platforms, correspond to manganic and ferric reduction.
Example IV
When M is the combination of Fe and Mn, the chemical formula of the positive electrode is AnFexMn1-x(OH)qX1-qLm, when A is Na, X F, L
For O2CC6H4CO2, x=0.5, n=1, when q=0.8, m=1, the molecular formula of corresponding positive electrode is NaFe0.5Mn0.5(OH)0.8F0.2
(O2CC6H4CO2)。
The present embodiment provides cage positive electrode NaFe0.5Mn0.5(OH)0.8F0.2(O2CC6H4CO2) preparation method, the party
Method includes the following steps：
（1）By NaClO4、Fe(ClO4)2、Mn(ClO4)2, 1,4- phthalic acids and NaF be according to stoichiometric ratio 1~3：0.5：
0.5：1：0.2 is dispersed in dimethylformamide, stirring；The wherein a concentration of 0.05-0.5 mol/L of ferrous perchlorate's solution,
Sodium perchlorate, ferrous perchlorate, Manganese perchlorate, 1,4- phthalic acids and sodium fluoride stoichiometric ratio 1~3：0.5：0.5：1：
0.2。
（2）It is transferred to polytetrafluoroethyllining lining after stirring evenly to obtain in stainless steel cauldron, 1-3 is kept the temperature at 120~150 DEG C
It；
（3）By the product of gained after filtering is washed, it is dried in vacuo 15-30 hours at 100-150 DEG C, obtains final product.
The NaFe that will be obtained0.5Mn0.5(OH)0.8F0.2(O2CC6H4CO2) metal ion battery is prepared, step is：It will
NaFe0.5Mn0.5(OH)0.8F0.2(O2CC6H4CO2), carbon black Super-P, PVDF and NMP be mixed and made into slurry, be coated on aluminium foil
On, 1cm is cut into compacting2Disk；Using the disk as anode, then use sodium metal as cathode, glass fiber filter paper as every
Film, NaPF6EC/DEC solution be electrolyte, dress up button cell.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (10)
1. a kind of cage positive electrode, it is characterised in that：The chemical formula of the positive electrode is AnM(OH)qX1-qLm,
Wherein A is any one in Na, K, Ca, Mg, Al or Zn,
M is at least one of Cr, Mn, Fe, Co, Ni or Cu,
X is F, Cl, Br, CO, CO3、 S、SO3Or SO4In any one,
L is CH3COO、O2CC6H4CO2、C5H5N、(CH3)2Any one in NC (O) H or CN,
0≤n≤2,0<q<1,0<m≤3.
2. a kind of cage positive electrode as described in claim 1, it is characterised in that：A be Na or K, M be Fe and Mn combination,
One kind in Fe, Mn, X F, Cl or SO4In one kind, L O2CC6H4CO2、C5H5One kind in N or CN.
3. a kind of cage positive electrode as described in claim 1, it is characterised in that：The microstructure of the cage positive electrode is
M forms MO with oxygen6Octahedron, MO6Octahedron forms parallel chain, chain MO by corner-sharing6Big lead to is formed by L is crosslinked
Road.
4. a kind of cage positive electrode as claimed in claim 2, it is characterised in that：When M is the combination of Fe and Mn, the anode
The chemical formula of material is AnFexMn1-x(OH)qX1-qLm, wherein 0<x<1,0≤n≤2,0<q<1,0<m≤3.
5. a kind of cage positive electrode as claimed in claim 4, it is characterised in that：When X is F, L O2CC6H4CO2When, this is just
The chemical formula of pole material is AnFexMn1-x(OH)qF1-q(O2CC6H4CO2)m, wherein A be Na or K, 0<x<1,0<N≤2,0<q<1,0
<m≤3。
6. a kind of preparation method of cage positive electrode as claimed in claim 5, which is characterized in that this method includes following step
Suddenly：
（1）Perchlorate, ferrous perchlorate, Manganese perchlorate, 1,4- phthalic acids and fluoride salt are dispersed in dimethylformamide
In, stirring；
（2）Polytetrafluoroethyllining lining is transferred to after stirring evenly to obtain in stainless steel cauldron in isothermal holding；
（3）By the product of gained after filtering is washed, vacuum drying obtains final product.
7. a kind of preparation method of cage positive electrode as claimed in claim 6, it is characterised in that：Work as positive electrode
AnFexMn1-x(OH)qF1-q(O2CC6H4CO2)mIn A be Na when, perchlorate NaClO4, fluoride salt NaF；It is high when A is K
Chlorate is KClO4, fluoride salt KF.
8. a kind of preparation method of cage positive electrode as claimed in claim 6, it is characterised in that：Step（2）At middle heat preservation
The temperature of reason is 120~150 DEG C, step（3）In vacuum drying temperature be 100-150 DEG C.
9. a kind of application of cage positive electrode as described in claim 1-5 any one, it is characterised in that：By the anode material
Material is used to prepare the anode of metal ion battery, and positive electrode, carbon black Super-P, PVDF and NMP are mixed and made into slurry, applies
It is overlying on aluminium foil, disk is cut into compacting, obtains anode.
10. a kind of application of cage positive electrode as claimed in claim 9, it is characterised in that：Using the disk as anode, potassium
For metal as cathode, for glass fiber filter paper as diaphragm, the EC/DEC solution of hexafluorophosphate is electrolyte, dresses up button electricity
Pond.
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