CN108615932A - Negative and positive double ion rocking chair type secondary cell and preparation method thereof - Google Patents
Negative and positive double ion rocking chair type secondary cell and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- 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
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to a kind of negative and positive double ion rocking chair type secondary cell, including anode, cathode, diaphragm and electrolyte, positive electrode includes transition metal oxide, general formula AXMYOZ, wherein A is Li, Na or K, one or more of M Cr, Mn, Ni, Co, Fe and Cu, and 0.1<X<2,0.01<Y<3,1<Z<7.The present invention also provides a kind of preparation methods of above-mentioned negative and positive double ion rocking chair type secondary cell, include the following steps：Positive electrode, negative material and diaphragm are processed into slabbing；It is put into diaphragm between a positive electrode and a negative electrode and electrolyte is added, obtains negative and positive double ion rocking chair type secondary cell.The negative and positive double ion rocking chair type secondary cell of the present invention may be implemented zwitterion and carry out reversible deintercalation in oxide anode material simultaneously, to which the capacity of battery be greatly improved.
Description
Technical field
The present invention relates to electrochemical storage field more particularly to a kind of negative and positive double ion rocking chair type secondary cell and its preparations
Method.
Background technology
Traditional " rocking chair type " secondary cell, such as lithium ion battery, sodium-ion battery and kalium ion battery are all to pass through alkali
Reversibly deintercalation is between positive and negative pole material as charge carrier for metal cation, to realize charge and discharge.The reason of this battery
It is determined by the alkali metal cation quantity of deintercalation by capacity, and this power-carrying value limits always the development of battery industry.
Although having there is document report carbon material that the deintercalation of anion, commercialized transition metal oxide anode may be implemented
Whether can realize that anion deintercalation not yet has been reported that.If zwitterion deintercalation simultaneously can be realized, this will make the appearance of battery
Tremendous increase is measured, and then pushes the development of entire battery industry.
Traditional its general formula of transition metal oxide material is AXMYOZ, wherein A=Li, Na or K, M=Cr, Mn, Ni,
Co, Fe, Cu or its multiplexed combination, and 0.1<X<2,0.01<Y<3,1<Z<7.The traditional alkali metal cation of this material participates in
The electrochemical mechanism equation of reaction is as follows：
Its theoretical capacity formula is CA=96500 α/3.6m(AXMYOZ), wherein m(AXMYOZ)For AXMYOZIf molecular weight it is cloudy
If cation can simultaneously participate in electrochemical reaction, the specific capacity of battery will break through the independent alkali metal cation of tradition and be provided
Capacity, zwitterion simultaneously deintercalation electrochemical mechanism equation it is as follows：
In this case theoretical capacity formula is β=96500 C=C α+C (alpha+beta)/3.6m(AXMYOZ)。
There is not yet a kind of anode at present and can be achieved at the same time zwitterion and carries out reversible taking off deficient battery wherein.
Invention content
In order to solve the above technical problems, the object of the present invention is to provide a kind of negative and positive double ion rocking chair type secondary cell and its
Zwitterion may be implemented simultaneously in oxide anode material in preparation method, negative and positive double ion rocking chair type secondary cell of the invention
It is middle to carry out reversible deintercalation, to which the capacity of battery be greatly improved.
A kind of negative and positive double ion rocking chair type secondary cell of the present invention, including positive electrode, negative material, diaphragm and electrolysis
Liquid, positive electrode include transition metal oxide, general formula AXMYOZ, wherein A is Li, Na or K, M Cr, Mn, Ni, Co, Fe
One or more of with Cu, and 0.1<X<2,0.01<Y<3,1<Z<7.
Preferably, transition metal oxide Na0.5Ni0.25Mn0.75O2。
Further, the grain size of transition metal oxide is 50-30000nm.Preferably, grain size 100-3000nm.
Further, negative material includes metal or carbon materials.
Further, negative material is lithium metal, metallic sodium, metallic potassium, graphite, hard carbon or soft carbon.
Further, electrolyte includes alkali metal salt and carbonate based organic solvent.
Further, the cation in alkali metal salt is independently selected from Li+、Na+Or K+, in the alkali metal salt it is cloudy from
Son is independently selected from ClO4 -、PF6 -Or BF4 -.Specifically, alkali metal salt is LiClO4、NaClO4、KClO4、LiPF6、NaPF6、
KPF6、LiBF4、NaBF4Or KBF4。
Further, carbonate based organic solvent is ethylene carbonate, propene carbonate, diethyl carbonate, carbonic acid diformazan
One or more of ester and methyl ethyl carbonate.
Further, a concentration of 0.1-10molL of electrolyte-1.Preferably, a concentration of 1molL of electrolyte-1。
Further, diaphragm is glass fibre membrane or cellguard diaphragms.
Further, the preparation method of transition metal oxide includes the following steps：.
(1) metal salt is soluble in water, it is heated after chelating agent is added thereto to eliminate moisture content, obtains solid material；Its
In, metal salt include the first metal salt and the second metal salt, the first metal salt be lithium salts, sodium salt or sylvite in one kind, second
Metal salt is one or more of manganese salt, nickel salt, cobalt salt, mantoquita, molysite and chromic salts；
(2) solid material is calcined 1-10 hours at 200-500 DEG C, then by the remaining solid after calcining in 600-1100
DEG C calcining 5-48h, obtain transition metal oxide.
Further, chelating agent is one or more of glycine, glutamic acid and citric acid.Chelating agent is used for Ao Hejin
Belong to the metal cation in sample.
Further, the molar ratio of the first metal salt and the second metal salt is 0.1-1:1.
Further, the molar ratio of chelating agent and metal salt is 1:1-10.
Preferably, the first metal salt is sodium salt.
Further, lithium salts is one or more of lithium carbonate, lithium nitrate, lithium acetate and lithium chloride.
Further, sylvite is one or more of potassium carbonate, potassium nitrate, potassium acetate and potassium chloride.
Further, sodium salt is one or more of sodium carbonate, sodium nitrate, sodium acetate and sodium chloride.
Further, manganese salt is one or more of manganese carbonate, manganese nitrate, manganese acetate and manganese chloride.
Further, nickel salt is one or more of nickelous carbonate, nickel nitrate, nickel acetate and nickel chloride.
Further, cobalt salt is one or more of cobalt carbonate, cobalt nitrate, cobalt acetate and cobalt chloride.
Further, mantoquita is one or more of copper carbonate, copper nitrate, copper acetate and copper chloride.
Further, molysite is one or more of ferric carbonate, ferric nitrate, ferric acetate and iron chloride.
Further, chromic salts is one or more of chromium carbonate, chromic nitrate, chromic acetate and chromium chloride.
Further, when calcining, heating rate is 1-30 DEG C/min.
Further, it is carried out under oxygen atmosphere, air atmosphere, argon gas atmosphere, nitrogen atmosphere or helium atmosphere when calcining.
Further, in positive electrode further include conductive agent and binder.
Further, when negative material includes carbon materials, negative material further includes conductive agent and binder.
Further, conductive agent is acetylene black, SPUER P, carbon black, Ketjen black, electrically conductive graphite, carbon fiber, carbon nanotube
One or more of with graphene.
Further, binder be Kynoar, polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, polyolefin, SBR rubber,
One or more of Viton and Polyurethane.
The negative and positive double ion rocking chair type secondary cell of the present invention, alkali metal cation and anion are in transition metal oxide
In can realize deintercalation, to realize that battery specific capacity is obviously improved.The negative and positive double ion rocking chair type secondary cell of the present invention
In charging, alkali metal cation is deviate from from transition metal oxide, anion embedded transiting metal oxidation from electrolyte
In object；When electric discharge, anion is deviate from from transition metal oxide to electrolyte, and alkali metal cation was embedded in from electrolyte
It crosses in metal oxide；It is always that alkali metal is embedded in cathode in terms of cathode.Both positive and negative charge carrier, it is reversible in battery
Deintercalation, the negative and positive double ion rocking chair type secondary cell of guarantee break through the limitation of traditional theory capacity in use, improve electricity
Pond power-carrying increases battery durable ability, pushes the development of battery industry.
The present invention also provides a kind of preparation methods of above-mentioned negative and positive double ion rocking chair type secondary cell, including following step
Suddenly：
(1) positive electrode, negative material and diaphragm are processed into slabbing；
(2) it is put into diaphragm between positive electrode and negative material and electrolyte is added, obtains negative and positive double ion rocking chair type
Secondary cell.
Further, further include being coated on paillon after mixing positive electrode, conductive agent and binder in step (1)
On, the step as anode.
Further, further include by negative material, conductive agent when negative material includes carbon materials in step (1)
It is coated on paillon after being mixed with binder, the step of as cathode.Further, paillon is copper foil or aluminium foil.
Further, in step (1), positive electrode or negative material are processed into the disk of a diameter of 6-18mm.
Further, in step (2), a concentration of 0.1-10molL of electrolyte-1.The volume of electrolyte is 0.01-
0.5mL。
According to the above aspect of the present invention, the present invention has at least the following advantages：
(1) negative and positive double ion rocking chair type secondary cell of the present invention has two kinds of charge carriers of zwitterion, realizes negative and positive
Ion common deintercalation in transition metal oxide is greatly improved by two kinds of carrier simultaneous transmission charges of zwitterion
Battery specific capacity, this negative and positive double ion rocking chair type secondary cell is in 20mAg-1Under discharge current, possess 180mAh g-1Ratio
Capacity.
(2) negative and positive double ion rocking chair type secondary cell of the present invention has high electrochemical specific capacity, wherein anion deintercalation flat
Platform improves the average working voltage of battery in 4V or more.
(3) negative and positive double ion rocking chair type secondary cell of the present invention has good specific capacity, high rate capability and cycle steady
Qualitative, future has broad application prospects in power battery field.
Above description is only the general introduction of technical solution of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, below with presently preferred embodiments of the present invention and after coordinating attached drawing to be described in detail such as.
Description of the drawings
Fig. 1 is Na used in the embodiment of the present invention 10.5Ni0.25Mn0.75O2Scanning electron microscopic picture；
Fig. 2 is Na used in the embodiment of the present invention 10.5Ni0.25Mn0.75O2X-ray powder diffraction pattern；
Fig. 3 is the typical charging and discharging curve of the negative and positive double ion rocking chair type secondary cell made by the embodiment of the present invention 1；
Fig. 4 is negative and positive double ion rocking chair type secondary cell made by the embodiment of the present invention 1 under 500mA/g current densities
Long circulating performance curve；
Fig. 5 is the typical charging and discharging curve of the negative and positive double ion rocking chair type secondary cell made by the embodiment of the present invention 4；
Fig. 6 is the typical charging and discharging curve of the negative and positive double ion rocking chair type secondary cell made by comparative example 5 of the present invention.
Specific implementation mode
With reference to the accompanying drawings and examples, the specific implementation mode of the present invention is described in further detail.Implement below
Example is not limited to the scope of the present invention for illustrating the present invention.
Embodiment 1
(1) positive electrode：Based on mass fraction comprising 75% transition metal oxide Na0.5Ni0.25Mn0.75O2,
20% acetylene black conductor, 5% Kynoar binder.
Negative material：Metallic sodium piece.
Battery diaphragm：Glass fibre membrane.
Electrolyte：1mol L-1NaClO4Carbonic allyl ester solution.
It is coated on copper foil or aluminium foil after positive electrode, conductive agent and binder are mixed, as anode.By above-mentioned electrode
Glass fibre membrane is cut into the disk of a diameter of 19mm by the disk for cutting into a diameter of 12mm.
(2) in argon gas glove box assemble CR2032 button cells, battery case related accessory (negative electrode casing, shrapnel, gasket,
Anode cover) it is stainless steel.Above-mentioned battery material is assembled in the following order：Negative electrode casing, gasket, is born shrapnel
Pole sodium piece, diaphragm, anode and anode cover are added dropwise the electrolyte of 0.05mL, are pressed on buckle battery mouth sealer when adding diaphragm
Negative and positive double ion rocking chair type secondary cell.After battery installs, charge-discharge test is carried out.
In the present embodiment, transition metal oxide Na0.5Ni0.25Mn0.75O2Preparation method it is as follows：
Weigh the NaNO of 0.42g3, the six water nickel nitrates of 0.73g and the six water manganese nitrates of 2.15g be dissolved in the water of 25mL
In, 2.55g glycine is added with chelated mineral cation.Aqueous solution is placed in 100 DEG C of baking ovens, until the moisture content in solution
Evaporating completely obtains viscous solid, and viscous solid is placed in stainless steel beaker and is calcined 1 hour in 220 DEG C, remaining powder is collected
Powder is placed in Muffle furnace and is calcined 24 hours in 750 DEG C, obtains transition metal oxide Na by end0.5Ni0.25Mn0.75O2。
To Na0.5Ni0.25Mn0.75O2SEM characterizations are carried out, as a result as Fig. 1, Fig. 1 show Na0.5Ni0.25Mn0.75O2For stratiform
The size of grain structure, particle is 50-300nm.Fig. 2 is Na prepared by the above method0.5Ni0.25Mn0.75O2XRD curves, figure
Middle calculated curves indicate that the Fitting Calculation value, observed curves indicate that actual test value, bragg position indicate
The base peak of P3 structures, difference indicate the error of calculated value and actual test value, as seen from the figure, prepared by the above method
Na0.5Ni0.25Mn0.75O2With typical P3 layer structures.
Electrochemical property test is carried out to the negative and positive double ion rocking chair type secondary cell of above-mentioned making, as a result such as Fig. 3.From figure
3 can be seen that, the material is in 20mA g-1First discharge specific capacity under current density is 180mAhg-1, this capacity alreadys exceed
Independent sodium ion deintercalation can be provided specific capacity (134mAh g-1), illustrate that negative and positive double ion rocking chair type secondary cell really can be with
Greatly improve the specific capacity of battery.In 500mA g-1Battery still has 130mAh g under current density-1, illustrate good times
Rate performance.In Fig. 4, top curve represents charge and discharge coulombic efficiency, and lower curve represents the specific capacity of material, and Fig. 4 shows passing through
The specific capacity for crossing battery in the long-time charge and discharge cycles of 100 circles also has original 85%, and long charge and discharge follow battery herein
Remain high coulombic efficiency in ring, these results illustrate the negative and positive double ion rocking chair type secondary cell made by embodiment 1
Really there is superelevation specific capacity, high working voltage, high rate capability and preferable cyclical stability.
Embodiment 2
Transition metal oxide in step (1) is replaced with into Na0.67Co0.33Mn0.67O2, by the electrolyte in step (2)
Volume replaces with 0.5mL, according to the method for step (1)-(2) in embodiment 1, makes negative and positive double ion rocking chair type secondary cell.
Embodiment 3
Transition metal oxide in step (1) is replaced with into NaCoO2, according to the side of step (1)-(2) in embodiment 1
Method makes negative and positive double ion rocking chair type secondary cell.
Embodiment 4
Electrolyte in step (2) is replaced with into 1mol L-1NaPF6Ethylene carbonate and diethyl carbonate solution, press
According to the method for step (1)-(2) in embodiment 1, negative and positive double ion rocking chair type secondary cell is made.
Electrochemical property test is carried out to the negative and positive double ion rocking chair type secondary cell of above-mentioned making, as a result such as Fig. 5.From figure
5 can be seen that, the material is in 20mA g-1First discharge specific capacity under current density is 170mAh g-1, this capacity surpassed
It crosses independent sodium ion deintercalation and can be provided specific capacity (134mAh g-1), illustrate the secondary electricity of negative and positive double ion rocking chair type of the present invention
Pond can greatly improve the specific capacity of battery really.
Embodiment 5
Electrolyte in step (2) is replaced with into 1mol L-1NaBF4Carbonic allyl ester solution, according to being walked in embodiment 1
Suddenly the method for (1)-(2) produces negative and positive double ion rocking chair type secondary cell.
Electrochemical property test is carried out to the negative and positive double ion rocking chair type secondary cell of above-mentioned making, as a result such as Fig. 6.From figure
6 can be seen that, the material is in 20mA g-1First discharge specific capacity under current density is 155mAh g-1, this capacity surpassed
It crosses independent sodium ion deintercalation and can be provided specific capacity (134mAh g-1), illustrate the secondary electricity of negative and positive double ion rocking chair type of the present invention
Pond can greatly improve the specific capacity of battery really.
Embodiment 6
Negative material in step (1) is replaced with into hard carbon, hard carbon is coated on after needing first and conductive agent to be mixed with binder
On copper foil or aluminium foil, according to the method for step (1)-(2) in embodiment 1, negative and positive double ion rocking chair type secondary cell is produced.
Embodiment 7
Transition metal oxide in step (1) is replaced with into LiCoO2, the negative material in step (1) is replaced with into gold
Belong to lithium, the electrolyte in step (2) is replaced with into 0.1mol L-1LiBF4Carbonic allyl ester solution, according to being walked in embodiment 1
Suddenly the method for (1)-(2) produces negative and positive double ion rocking chair type secondary cell.
Embodiment 8
Transition metal oxide in step (1) is replaced with into LiCoO2, the negative material in step (1) is replaced with into stone
Ink, graphite are coated on copper foil or aluminium foil after needing first and conductive agent to be mixed with binder, the electrolyte in step (2) are replaced with
1molL-1LiPF6Carbonic allyl ester solution produce negative and positive double ion according to the method for step (1)-(2) in embodiment 1 and shake
Chair form secondary cell.
Embodiment 9
Transition metal oxide in step (1) is replaced with into KCoO2, the negative material in step (1) is replaced with into gold
Belong to potassium, the electrolyte in step (2) is replaced with into 1mol L-1KBF4Carbonic allyl ester solution, according to step in embodiment 1
(1) method of-(2) produces negative and positive double ion rocking chair type secondary cell.
Embodiment 10
Transition metal oxide in step (1) is replaced with into KMnO2, the negative material in step (1) is replaced with firmly
Carbon, hard carbon are coated on copper foil or aluminium foil after needing first and conductive agent to be mixed with binder, the electrolyte in step (2) are replaced with
1molL-1KClO4Methyl ethyl carbonate ester solution produce negative and positive double ion according to the method for step (1)-(2) in embodiment 1 and shake
Chair form secondary cell.
Embodiment 11
Transition metal oxide in step (1) is replaced with into Na0.1Co0.1Mn0.9O2, by the electrolyte in step (2)
Product replaces with 0.01mL, according to the method for step (1)-(2) in embodiment 1, makes negative and positive double ion rocking chair type secondary cell.
Embodiment 12
Transition metal oxide in step (1) is replaced with into Na0.67Co0.01Fe0.33Mn0.66O2, by the electricity in step (2)
Solution liquid product replaces with 0.1mL, according to the method for step (1)-(2) in embodiment 1, makes the secondary electricity of negative and positive double ion rocking chair type
Pond.
Embodiment 13
Transition metal oxide in step (1) is replaced with into Na2Mn3O7, the electrolyte volume in step (2) is replaced
For 0.1mL negative and positive double ion rocking chair type secondary cell is made according to the method for step (1)-(2) in embodiment 1.
In conclusion the negative and positive double ion rocking chair type secondary cell of the present invention, can greatly improve battery specific capacity, and
With high operating voltage, high rate capability and high cyclical stability.The negative and positive double ion rocking chair type two of this method assembling
Primary cell has a good application prospect on energy storage device.
The above is only a preferred embodiment of the present invention, it is not intended to restrict the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is several improvement and
Modification, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of negative and positive double ion rocking chair type secondary cell, including positive electrode, negative material, diaphragm and electrolyte, feature
It is：The positive electrode includes transition metal oxide, general formula AXMYOZ, wherein A be Li, Na or K, M Cr, Mn,
One or more of Ni, Co, Fe and Cu, and 0.1<X<2,0.01<Y<3,1<Z<7.
2. negative and positive double ion rocking chair type secondary cell according to claim 1, it is characterised in that：The transiting metal oxidation
The grain size of object is 50-30000nm.
3. negative and positive double ion rocking chair type secondary cell according to claim 1, it is characterised in that：Negative material includes metal
Or carbon materials.
4. negative and positive double ion rocking chair type secondary cell according to claim 1, it is characterised in that：Negative material is metal
Lithium, metallic sodium, metallic potassium, graphite, hard carbon or soft carbon.
5. negative and positive double ion rocking chair type secondary cell according to claim 1, it is characterised in that：The electrolyte includes alkali
Metal salt and carbonate based organic solvent.
6. negative and positive double ion rocking chair type secondary cell according to claim 5, it is characterised in that：In the alkali metal salt
Cation is independently selected from Li+、Na+Or K+, the anion in the alkali metal salt is independently selected from ClO4 -、PF6 -Or BF4 -。
7. negative and positive double ion rocking chair type secondary cell according to claim 5, it is characterised in that：The carbonates are organic
Solvent is one or more of ethylene carbonate, propene carbonate, diethyl carbonate, dimethyl carbonate and methyl ethyl carbonate.
8. negative and positive double ion rocking chair type secondary cell according to claim 1, which is characterized in that the transiting metal oxidation
The preparation method of object includes the following steps：.
(1) metal salt is soluble in water, it is heated after chelating agent is added thereto to eliminate moisture content, obtains solid material；Wherein, institute
It includes the first metal salt and the second metal salt to state metal salt, and first metal salt is one kind in lithium salts, sodium salt or sylvite, institute
It is one or more of manganese salt, nickel salt, cobalt salt, mantoquita, molysite and chromic salts to state the second metal salt；
(2) solid material is calcined 1-10 hours at 200-500 DEG C, then by the remaining solid after calcining in 600-1100
DEG C calcining 5-48h, obtain the transition metal oxide.
9. negative and positive double ion rocking chair type secondary cell according to claim 8, it is characterised in that：The chelating agent is sweet ammonia
One or more of acid, glutamic acid and citric acid.
10. the preparation method of the negative and positive double ion rocking chair type secondary cell described in any one of claim 1-9, feature exist
In including the following steps：
(1) positive electrode, negative material and diaphragm are processed into slabbing；
(2) be put into diaphragm between the positive electrode and negative material and the electrolyte be added, obtain the negative and positive it is double from
Sub- rocking chair type secondary cell.
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| CN109904452A (en) * | 2019-02-21 | 2019-06-18 | 三峡大学 | The preparation method of sodium base Dual-ion cell based on carbon fiber negative electrode material |
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