CN109920979A - Positive plate and electrochemical cell - Google Patents
Positive plate and electrochemical cell Download PDFInfo
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- CN109920979A CN109920979A CN201711318082.4A CN201711318082A CN109920979A CN 109920979 A CN109920979 A CN 109920979A CN 201711318082 A CN201711318082 A CN 201711318082A CN 109920979 A CN109920979 A CN 109920979A
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- prussian blue
- positive
- positive plate
- blue material
- sodium
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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 application provides a positive plate and an electrochemical cell. The positive plate comprises a positive current collector and a positive membrane, the positive membrane is arranged on the positive current collector and comprises a positive active material, the positive active material comprises a Prussian blue material-conductive additive compound, and the molecular formula of the Prussian blue material is AxMy[M′(CN)6]zWherein A is one or more of alkali metal cations and alkaline earth metal cations, M is transition metal, M' is transition metal, x is more than 0 and less than or equal to 2, y is more than 0 and less than or equal to 1, z is more than 0 and less than or equal to 1, and the resistivity of the positive electrode membrane is less than or equal to 400 omega cm. The resistivity of the anode membrane is controlled within a certain range, so that the conductivity of the anode membrane can be effectively improved, the capacity exertion of Prussian blue materials is facilitated, and the electrochemical cell has good rate performance, high initial capacity and good cycle performance.
Description
Technical field
This application involves field of batteries more particularly to a kind of positive plates and electrochemical cell.
Background technique
Lithium ion battery is widely applied with the advantages that its high-energy density, long circulation life, but lithium ion battery
Problems are still suffered from, wherein cost problem becomes the one of the major reasons for restricting its development.It is possible to replace as one kind
For the electrochemical energy storage system of new generation of existing energy accumulating device, sodium-ion battery has obtained scientific research and industry in recent years
Greatly concern.The comprehensive performance of sodium-ion battery how is promoted, can realize that commercially producing is current important grind
Originating party to.
Summary of the invention
In view of the problems in the background art, the application is designed to provide a kind of positive plate and electrochemical cell,
The electrochemical cell takes into account preferable high rate performance, higher initial capacity and good cycle performance.
In order to achieve the above object, in the one side of the application, this application provides a kind of positive plates comprising anode collection
Fluid and positive diaphragm, the anode diaphragm are set on the plus plate current-collecting body, and the anode diaphragm includes positive-active
Material, the positive electrode active materials include prussian blue material-conductive additive compound, the prussian blue material
Molecular formula is AxMy[M′(CN)6]z, wherein A is one or more of alkali metal cation, alkaline earth metal cation, and M was
Metal is crossed, M ' is transition metal, and 0 < x≤2,0 < y≤1,0 z≤1 <, the resistivity of the anode diaphragm is less than or equal to 400
Ω·cm。
In the another aspect of the application, this application provides a kind of electrochemical cells comprising the application one side is just
Pole piece.
Compared with the existing technology, the application has the beneficial effect that
The electrochemical cell of the application selects prussian blue material-conductive additive compound as positive-active material
Material, while in a certain range by the control of the resistivity of positive diaphragm, it can be effectively improved the high rate performance of electrochemical cell, together
When so that electrochemical cell is taken into account higher initial capacity and good cycle performance.
Specific embodiment
The following detailed description of the positive plate and electrochemical cell according to the application.
Illustrate the positive plate according to the application first aspect first.
Positive plate according to the application first aspect includes plus plate current-collecting body and positive diaphragm, the anode diaphragm setting
In on the plus plate current-collecting body, the anode diaphragm includes positive electrode active materials, and the positive electrode active materials include Prussian blue
Class material-conductive additive compound, the molecular formula of the prussian blue material are AxMy[M′(CN)6]z, wherein A is alkali
One or more of metal cation, alkaline earth metal cation, M are transition metal, and M ' is transition metal, 0 < x≤2,0 < y
≤ 1,0 z≤1 <.The resistivity of the anode diaphragm is less than or equal to 400 Ω cm, it is preferable that the resistivity of the anode diaphragm
For the 15 Ω cm of Ω cm~400, it is highly preferred that the resistivity of the anode diaphragm is 30 Ω of Ω cm~200 cm.
In the positive plate according to the application first aspect, the resistivity of positive diaphragm is controlled in a certain range
It is interior, the comprehensive performance of electrochemical cell can be significantly improved, electrochemical cell is made to take into account preferable high rate performance, higher initial
Capacity and good cycle performance.If the resistivity of positive diaphragm is excessively high, the electronics and ion in positive diaphragm are in charge and discharge
In the process inside positive electrode active materials particle, inside positive electrode active materials particle to positive electrode active materials particle surface, from
One positive electrode active materials particle surface to another positive electrode active materials particle surface, from positive electrode active materials particle to electrolysis
Liquid interface, the diffusion from positive electrode active materials particle to anode collection body interface etc. during a series of and transmission rate compared with
Slowly, so as to will lead to the dynamic performance of electrochemical cell, high rate performance and initial capacity poor.Simultaneously as general Shandong
The electronics and ionic conductivity of scholar's indigo plant class material itself are poor, the excessively high appearance that can also seriously affect prussian blue material of resistivity
Amount plays, and then can also seriously affect initial capacity, cycle performance and the high rate performance of electrochemical cell.
In the positive plate according to the application first aspect, the type of the conductive additive is not limited specifically
System, can be selected according to actual needs.Specifically, the conductive additive can be selected from inorganic conductive agent, in conducting polymer
One or more.Preferably, the conductive additive is the mixture of inorganic conductive agent and conducting polymer.
In the positive plate according to the application first aspect, if the content of inorganic conductive agent is excessive, due to its tool
There is stronger absorbency, can not usually be formed in the fabricated in situ of prussian blue material-conductive additive compound uniformly
The mobile phase of dispersion causes the feasibility for preparing compound and practicability poor；If the content of inorganic conductive agent is very few, can not
Achieve the purpose that improve electrochemical cell initial capacity, cycle performance and high rate performance.Preferably, the inorganic conductive agent contains
Amount is the 0.1%~5% of the prussian blue material-conductive additive compound gross mass, it is further preferred that the nothing
The content of machine conductive agent is the 0.5%~3% of the prussian blue material-conductive additive compound gross mass.
In the positive plate according to the application first aspect, if the content of conducting polymer is excessive, institute will lead to
The crystal structure and chemical composition existing defects of the prussian blue material of preparation, to influence the performance of its capacity, while general Shandong
The presence of defect also results in the reduction of its crystallinity, the i.e. degree of order drop of electronics and atomic arrangement in scholar's indigo plant class material crystal structure
It is low, to make diffusion and retard motion of the electronics in prussian blue material, and then it also will affect the resistivity of positive diaphragm；
If the content of conducting polymer is very few, being unable to reach improves electrochemical cell initial capacity, cycle performance and high rate performance
Purpose.Preferably, the content of the conducting polymer is the prussian blue material-conductive additive compound gross mass
0.1%~15%, it is further preferred that the content of the conducting polymer is the prussian blue material-conductive additive
The 1%~3% of compound gross mass.
In the positive plate according to the application first aspect, it is preferable that the inorganic conductive agent can be selected from acetylene black,
One of conductive black, Ketjen black, carbon nanotube, carbon fiber, carbon nanocoils, graphene, carbon nanobelts, electrically conductive graphite are several
Kind.
In the positive plate according to the application first aspect, it is preferable that the conducting polymer can be selected from polypyrrole,
One or more of polyaniline, polythiophene, polyphenylene sulfide and its derivative.Wherein it is preferable to use poly- ethylenes for polythiofuran derivative
Dioxy thiophene-poly styrene sulfonate (PEDOT/PSS).
In the positive plate according to the application first aspect, the anode diaphragm further includes conventional conductive agent and glues
Agent is tied, conventional conductive agent and binder are dispersed in positive diaphragm.Specifically, conventional conductive agent, prussian blue material
Material-conductive additive compound, binder are dispersed in solvent and anode sizing agent are made, and are formed just after drying and removing solvent
Pole diaphragm.The type of the conventional conductive agent does not limit specifically, can be selected according to actual needs.Specifically, described
Conventional conductive agent can be selected from one or more of acetylene black, Super-P, carbon nanotube, Ketjen black, electrically conductive graphite, these are often
The content of rule conductive agent is preferably greater than or equal to the 5% of the positive diaphragm gross mass, good to further provide in positive diaphragm
Good conductive channel controls the resistivity of positive diaphragm, so as to improve the performance of electrochemical cell.It is further preferred that described
The content of conventional conductive agent is the 5%~20% of the positive diaphragm gross mass.The type of the binder does not limit specifically
System, can be selected according to actual needs.Specifically, the binder can be selected from water-soluble binder, in oil-soluble binder
One or more.
In the positive plate according to the application first aspect, it is preferable that the partial size D50 of the prussian blue material
It is 0.5 μm~5 μm.The partial size of prussian blue material is larger, then can make electronics and ion in prussian blue material granule
The transmission path in portion extends, therefore will cause the conductive son of positive diaphragm and lead ionic reduction, and cathode film sheet resistivity is also higher；
The partial size of prussian blue material is smaller, although conductive son and lead it is ionic preferably, the knot of prussian blue material at this time
Brilliant degree is generally lower, and the defect of crystal structure and chemical composition increases, while the lesser prussian blue material of partial size is due to tool
There is higher specific surface area, it is serious to will lead to poor dispersion, imbibition phenomenon in anode sizing agent, while can also make positive diaphragm
Granular sensation is heavier, surface density is uneven, compacted density reduces, therefore the cycle life of electrochemical cell and security performance all can
It is affected.
In the positive plate according to the application first aspect, the prussian blue material is cube of highly crystalline
The phase structure perhaps unordered heap of hexagonal phase structure amorphous structure or the lower prussian blue material of crystallinity due to ion
Product can hinder the diffusion and transmission of electronics and ion, to will lead to the conductive son of positive diaphragm and lead ionic poor, cathode film
Sheet resistivity is higher, and the comprehensive performance of electrochemical cell is poor.
In the positive plate according to the application first aspect, it is described anode diaphragm with a thickness of 10 μm~200 μm, it is excellent
Selection of land, it is described anode diaphragm with a thickness of 60 μm~120 μm.The thickness of positive diaphragm is smaller, the energy density of electrochemical cell
It is lower；The thickness of positive diaphragm is larger, then positive diaphragm is easy to appear cracking, causes cathode film sheet resistivity to increase, thus shadow
The chemical property of electrochemical cell is rung, positive diaphragm is may cause under serious conditions and falls off from plus plate current-collecting body, cause electricity
Chemical cell can not normal use.
In the positive plate according to the application first aspect, the prussian blue material-conductive additive is compound
Object can be obtained by fabricated in situ.In the prussian blue material-conductive additive compound, conductive additive at least one
Part is coated on prussian blue material surface.
Preferably, if the conductive additive is inorganic conductive agent, prussian blue material-conductive additive compound
Preparation method can are as follows: solution one is made in the dissolution of precursor metal M salt in a solvent；Six cyanogen that metal M ' and metal A is formed
Base Metal salt and inorganic conductive agent are dissolved in acquisition solution two in solvent；Solution one and solution two are mixed, after reacting a period of time
Sediment is obtained, separates and collect sediment later, it is washed, dry, it is compound to obtain prussian blue material-conductive additive
Object.
Preferably, if the conductive additive is conducting polymer, prussian blue material-conductive additive compound
Preparation method can are as follows: solution one is made in the dissolution of precursor metal M salt in a solvent；Six cyanogen that metal M ' and metal A is formed
The monomer and initiator of Base Metal salt and synthesis conducting polymer are dissolved in acquisition solution two in solvent；By solution one and solution
Two mixing, obtain sediment after reacting a period of time, separate and collect sediment later, washed, dry, obtain Prussian blue
Class material-conductive additive compound.
Preferably, if the conductive additive is conducting polymer, prussian blue material-conductive additive compound
Preparation method may be used also are as follows: solution one is made in the dissolution of precursor metal M salt in a solvent；Six that metal M ' and metal A is formed
Cyano metal salt and the evenly dispersed acquisition solution two in a solvent of conductive polymer colloid；Solution one and solution two are mixed, instead
Sediment is obtained after answering a period of time, separates and collect sediment later, it is washed, dry, it obtains prussian blue material-and leads
Electric additive compound.
Secondly illustrate the electrochemical cell according to the application second aspect.
Electrochemical cell according to the application second aspect include according to the positive plate of the application first aspect, negative electrode tab,
Electrolyte and isolation film etc..
In the electrochemical cell according to the application second aspect, the electrochemical cell can for lithium ion battery,
Sodium-ion battery, kalium ion battery, Zinc ion battery or aluminium ion battery.In embodiments herein, electrochemistry is only shown
Battery is the embodiment of sodium-ion battery, but the application is without being limited thereto.
In sodium-ion battery, negative electrode tab may include negative current collector and be set on negative current collector and contain cathode
The cathode membrane of active material.The negative electrode active material can be selected from carbon material, alloy material, transition metal oxide and vulcanization
One or more of object, phosphorous-based materials, titanate material.Specifically, the carbon material can be selected from hard carbon, soft carbon, amorphous
One or more of carbon, nanostructured carbon material；The alloy material can be selected from one of Si, Ge, Sn, Pb, Sb or several
The alloy material that kind is formed；The general formula of the transition metal oxide and sulfide is MxNy, wherein M be Fe, Co, Ni, Cu, Mn,
The one or more of Sn, Mo, Sb, V, N are O or S；The phosphorous-based materials can be selected from one of red phosphorus, white phosphorus, black phosphorus or several
Kind；The titanate material can be selected from Na2Ti3O7、Na2Ti6O13、Na4Ti5O12、Li4Ti5O12、NaTi2(PO4)3One of or
It is several.
In sodium-ion battery, the negative electrode tab further includes conductive agent and binder, the kind of the conductive agent and binder
Class does not limit specifically, can be selected according to actual needs.
In sodium-ion battery, the electrolyte can be liquid electrolyte, and the electrolyte may include sodium salt, organic solvent
And optional electrolysis additive.The type of the sodium salt does not limit specifically, can be selected according to actual needs.Tool
Body, the sodium salt can be selected from sodium hexafluoro phosphate (NaPF6), sodium perchlorate (NaClO4), hexafluoro Boratex (NaBF6), fluoroform
One or more of base sodium sulfonate, trifluoromethane sulfonic acid imines sodium (NaTFSI).The type of the organic solvent is not specific
Limitation, can be selected according to actual needs.Specifically, the organic solvent can be selected from ethylene carbonate, propene carbonate,
One of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate are and several.The type of the electrolysis additive does not have
The limitation of body can be added selectively according to actual needs.
In sodium-ion battery, the material of the isolation film is unrestricted, can be selected according to actual needs.Specifically
Ground, isolation film can be selected from polypropylene screen, polyethylene film, polyethylene/polypropylene/polyethylene composite membrane, non-woven membrane, glass fibers
Tie up one of film.
Below with reference to embodiment, the application is further described.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.
Embodiment 1
(1) preparation of positive plate
By manganese chloride (MnCl2·4H2O it) is dissolved in deionized water, forms solution one；PEDOT/PSS is dispersed in
In deionized water, and sodium ferrocyanide (Na is added4Fe(CN)6·10H2O), solution two is formed；Solution one is slowly added dropwise to molten
It is reacted in liquid two, collects gained precipitating after reaction, add by washing, being drying to obtain prussian blue material-conductive
Add agent compound Na2MnFe(CN)6- PEDOT/PSS, wherein prussian blue material Na2MnFe(CN)6Partial size D50 be 1 μ
The content of m, conductive additive PEDOT/PSS are the 0.1% of the compound gross mass.
By the above-mentioned prussian blue material-conductive additive compound being prepared and conventional conductive agent Super P, glue
Tie agent polyvinylidene fluoride is that 80:10:10 is dissolved in solvent N-methyl pyrilidone in mass ratio, is thoroughly mixed uniformly
Afterwards, anode sizing agent is obtained；Then anode sizing agent is evenly applied on plus plate current-collecting body aluminium foil, later by drying, being cold-pressed, divide
Item obtains positive plate.
(2) preparation of negative electrode tab
Negative electrode active material hard carbon, conductive agent acetylene black, binder butadiene-styrene rubber (SBR) is molten for 90:5:5 in mass ratio
In deionized water, after being thoroughly mixed uniformly, negative electrode slurry is obtained；Then negative electrode slurry is applied coated with negative current collector copper foil
On, negative electrode tab is obtained by drying, cold pressing, slitting later.
(3) preparation of electrolyte
Isometric ethylene carbonate is dissolved in propene carbonate, is then dissolved in suitable sodium salt sodium perchlorate
In the mixed solvent obtains electrolyte.
(4) preparation of isolation film
Select polyethylene film as isolation film.
(5) preparation of sodium-ion battery
Battery core is made by winding in positive plate, negative electrode tab and isolation film, then battery core is fitted into battery packages shell, it
After inject electrolyte, using chemical conversion, stand etc. techniques be made sodium-ion battery.
Embodiment 2
With embodiment 1, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
The content of PEDOT/PSS is the 1% of prussian blue material-conductive additive compound gross mass, anode sizing agent
The quality of middle prussian blue material-conductive additive compound and conventional conductive agent Super P, binder polyvinylidene fluoride
Than for 80:10:10.
Embodiment 3
With embodiment 1, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
The content of PEDOT/PSS is the 3% of prussian blue material-conductive additive compound gross mass, anode sizing agent
The quality of middle prussian blue material-conductive additive compound and conventional conductive agent Super P, binder polyvinylidene fluoride
Than for 80:10:10.
Embodiment 4
With embodiment 1, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
The content of PEDOT/PSS is the 10% of prussian blue material-conductive additive compound gross mass, anode sizing agent
The quality of middle prussian blue material-conductive additive compound and conventional conductive agent Super P, binder polyvinylidene fluoride
Than for 80:10:10.
Embodiment 5
With embodiment 1, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
The content of PEDOT/PSS is the 15% of prussian blue material-conductive additive compound gross mass, anode sizing agent
The quality of middle prussian blue material-conductive additive compound and conventional conductive agent Super P, binder polyvinylidene fluoride
Than for 80:10:10.
Embodiment 6
With embodiment 1, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
By manganese chloride (MnCl2·4H2O it) is dissolved in deionized water, forms solution one；Polypyrrole is dispersed in
In ionized water, and sodium ferrocyanide (Na is added4Fe(CN)6·10H2O), solution two is formed；Solution one is slowly added dropwise to solution
It is reacted in two, collects gained precipitating after reaction, by washing, being drying to obtain the addition of prussian blue material-conductive
Agent compound Na2MnFe(CN)6Polypyrrole, wherein prussian blue material Na2MnFe(CN)6Partial size D50 be 1 μm, it is conductive
The content of additive polypyrrole is the 1% of the compound gross mass.
By the above-mentioned prussian blue material-conductive additive compound being prepared and conventional conductive agent Super P, glue
Tie agent polyvinylidene fluoride is that 80:10:10 is dissolved in solvent N-methyl pyrilidone in mass ratio, is thoroughly mixed uniformly
Afterwards, anode sizing agent is obtained；Then anode sizing agent is evenly applied on plus plate current-collecting body aluminium foil, later by drying, being cold-pressed, divide
Item obtains positive plate.
Embodiment 7
With embodiment 1, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
By manganese chloride (MnCl2·4H2O it) is dissolved in deionized water, forms solution one；Carbon nanotube is dispersed in
In deionized water, and sodium ferrocyanide (Na is added4Fe(CN)6·10H2O), solution two is formed；Solution one is slowly added dropwise to molten
It is reacted in liquid two, collects gained precipitating after reaction, add by washing, being drying to obtain prussian blue material-conductive
Add agent compound Na2MnFe(CN)6Carbon nanotube, wherein prussian blue material Na2MnFe(CN)6Partial size D50 be 1 μm,
The content of conductive additive carbon nanotube is the 1% of the compound gross mass.
By the above-mentioned prussian blue material-conductive additive compound being prepared and conventional conductive agent Super P, glue
Tie agent polyvinylidene fluoride is that 80:10:10 is dissolved in solvent N-methyl pyrilidone in mass ratio, is thoroughly mixed uniformly
Afterwards, anode sizing agent is obtained；Then anode sizing agent is evenly applied on plus plate current-collecting body aluminium foil, later by drying, being cold-pressed, divide
Item obtains positive plate.
Embodiment 8
With embodiment 1, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
By manganese chloride (MnCl2·4H2O it) is dissolved in deionized water, forms solution one；Polypyrrole, carbon nanotube is uniform
It is scattered in deionized water, and sodium ferrocyanide (Na is added4Fe(CN)6·10H2O), solution two is formed；Solution one is slowly dripped
It adds in solution two and is reacted, gained precipitating is collected after reaction, by washing, being drying to obtain prussian blue material-
Conductive additive compound Na2MnFe(CN)6Polypyrrole/carbon nanotube, wherein prussian blue material Na2MnFe(CN)6's
Partial size D50 is 1 μm, and the content of conductive additive polypyrrole is the 0.5% of the compound gross mass, conductive additive carbon nanotube
Content be the compound gross mass 0.5%.
By the above-mentioned prussian blue material-conductive additive compound being prepared and conventional conductive agent Super P, glue
Tie agent polyvinylidene fluoride is that 80:10:10 is dissolved in solvent N-methyl pyrilidone in mass ratio, is thoroughly mixed uniformly
Afterwards, anode sizing agent is obtained；Then anode sizing agent is evenly applied on plus plate current-collecting body aluminium foil, later by drying, being cold-pressed, divide
Item obtains positive plate.
Embodiment 9
With embodiment 1, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
By manganese chloride (MnCl2·4H2O it) is dissolved in deionized water, forms solution one；Polyaniline is dispersed in
In ionized water, and sodium ferrocyanide (Na is added4Fe(CN)6·10H2O), solution two is formed；Solution one is slowly added dropwise to solution
It is reacted in two, collects gained precipitating after reaction, by washing, being drying to obtain the addition of prussian blue material-conductive
Agent compound Na2MnFe(CN)6Polyaniline, wherein prussian blue material Na2MnFe(CN)6Partial size D50 be 1 μm, it is conductive
The content of additive polyaniline is the 3% of the compound gross mass.
By the above-mentioned prussian blue material-conductive additive compound being prepared and conventional conductive agent Super P, glue
Tie agent polyvinylidene fluoride is that 80:10:10 is dissolved in solvent N-methyl pyrilidone in mass ratio, is thoroughly mixed uniformly
Afterwards, anode sizing agent is obtained；Then anode sizing agent is evenly applied on plus plate current-collecting body aluminium foil, later by drying, being cold-pressed, divide
Item obtains positive plate.
Embodiment 10
With embodiment 1, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
By manganese chloride (MnCl2·4H2O it) is dissolved in deionized water, forms solution one；Ketjen black is dispersed in
In ionized water, and sodium ferrocyanide (Na is added4Fe(CN)6·10H2O), solution two is formed；Solution one is slowly added dropwise to solution
It is reacted in two, collects gained precipitating after reaction, by washing, being drying to obtain the addition of prussian blue material-conductive
Agent compound Na2MnFe(CN)6Ketjen black, wherein prussian blue material Na2MnFe(CN)6Partial size D50 be 1 μm, it is conductive
The content of additive Ketjen black is the 1% of the compound gross mass.
By the above-mentioned prussian blue material-conductive additive compound being prepared and conventional conductive agent Super P, glue
Tie agent polyvinylidene fluoride is that 80:10:10 is dissolved in solvent N-methyl pyrilidone in mass ratio, is thoroughly mixed uniformly
Afterwards, anode sizing agent is obtained；Then anode sizing agent is evenly applied on plus plate current-collecting body aluminium foil, later by drying, being cold-pressed, divide
Item obtains positive plate.
Embodiment 11
With embodiment 1, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
By manganese chloride (MnCl2·4H2O it) is dissolved in deionized water, forms solution one；Carbon nanotube is dispersed in
In deionized water, and sodium ferrocyanide (Na is added4Fe(CN)6·10H2O), solution two is formed；Solution one is slowly added dropwise to molten
It is reacted in liquid two, collects gained precipitating after reaction, add by washing, being drying to obtain prussian blue material-conductive
Add agent compound Na2MnFe(CN)6Carbon nanotube, wherein prussian blue material Na2MnFe(CN)6Partial size D50 be 1 μm,
The content of conductive additive carbon nanotube is the 3% of the compound gross mass.
By the above-mentioned prussian blue material-conductive additive compound being prepared and conventional conductive agent Super P, glue
Tie agent polyvinylidene fluoride is that 80:10:10 is dissolved in solvent N-methyl pyrilidone in mass ratio, is thoroughly mixed uniformly
Afterwards, anode sizing agent is obtained；Then anode sizing agent is evenly applied on plus plate current-collecting body aluminium foil, later by drying, being cold-pressed, divide
Item obtains positive plate.
Embodiment 12
With embodiment 1, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
By manganese chloride (MnCl2·4H2O it) is dissolved in deionized water, forms solution one；Carbon nanotube is dispersed in
In deionized water, and sodium ferrocyanide (Na is added4Fe(CN)6·10H2O), solution two is formed；Solution one is slowly added dropwise to molten
It is reacted in liquid two, collects gained precipitating after reaction, add by washing, being drying to obtain prussian blue material-conductive
Add agent compound Na2MnFe(CN)6Carbon nanotube, wherein prussian blue material Na2MnFe(CN)6Partial size D50 be 1 μm,
The content of conductive additive carbon nanotube is the 5% of the compound gross mass.
By the above-mentioned prussian blue material-conductive additive compound being prepared and conventional conductive agent Super P, glue
Tie agent polyvinylidene fluoride is that 80:10:10 is dissolved in solvent N-methyl pyrilidone in mass ratio, is thoroughly mixed uniformly
Afterwards, anode sizing agent is obtained；Then anode sizing agent is evenly applied on plus plate current-collecting body aluminium foil, later by drying, being cold-pressed, divide
Item obtains positive plate.
Embodiment 13
With embodiment 2, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
Prussian blue material Na2MnFe(CN)6Partial size D50 be 0.4 μm.
Embodiment 14
With embodiment 2, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
Prussian blue material Na2MnFe(CN)6Partial size D50 be 0.5 μm.
Embodiment 15
With embodiment 2, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
Prussian blue material Na2MnFe(CN)6Partial size D50 be 2 μm.
Embodiment 16
With embodiment 2, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
Prussian blue material Na2MnFe(CN)6Partial size D50 be 5 μm.
Embodiment 17
With embodiment 2, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
Prussian blue material Na2MnFe(CN)6Partial size D50 be 6 μm.
Embodiment 18
With embodiment 2, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
Prussian blue material-conductive additive compound, conventional conductive agent Super P, binder are poly- in anode sizing agent
The mass ratio of vinylidene fluoride is 85:5:10.
Embodiment 19
With embodiment 2, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
Prussian blue material-conductive additive compound, conventional conductive agent Super P, binder are poly- in anode sizing agent
The mass ratio of vinylidene fluoride is 70:20:10.
Embodiment 20
With embodiment 2, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
The prussian blue material-conductive additive compound and conventional conductive agent carbon nanometer that embodiment 2 is prepared
Pipe, binder polyvinylidene fluoride are that 80:10:10 is dissolved in solvent N-methyl pyrilidone in mass ratio, are thoroughly mixed
After uniformly, anode sizing agent is obtained；Then anode sizing agent is evenly applied on plus plate current-collecting body aluminium foil, passes through later and dries, is cold
Pressure, slitting obtain positive plate.
Embodiment 21
With embodiment 2, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
Prussian blue material-conductive additive compound that embodiment 2 is prepared and conventional conductive agent Ketjen black,
Binder polyvinylidene fluoride is that 80:10:10 is dissolved in solvent N-methyl pyrilidone in mass ratio, is thoroughly mixed uniformly
Afterwards, anode sizing agent is obtained；Then anode sizing agent is evenly applied on plus plate current-collecting body aluminium foil, later by drying, being cold-pressed, divide
Item obtains positive plate.
Embodiment 22
With embodiment 2, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
Prussian blue material-conductive additive compound that embodiment 2 is prepared and conventional conductive agent acetylene black,
Binder polyvinylidene fluoride is that 80:10:10 is dissolved in solvent N-methyl pyrilidone in mass ratio, is thoroughly mixed uniformly
Afterwards, anode sizing agent is obtained；Then anode sizing agent is evenly applied on plus plate current-collecting body aluminium foil, later by drying, being cold-pressed, divide
Item obtains positive plate.
Comparative example 1
With embodiment 1, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
The content of PEDOT/PSS is the 20% of prussian blue material-conductive additive compound gross mass, anode sizing agent
The quality of middle prussian blue material-conductive additive compound and conventional conductive agent Super P, binder polyvinylidene fluoride
Than for 80:10:10.
Comparative example 2
The content of PEDOT/PSS is the 0.05% of prussian blue material-conductive additive compound gross mass, anode slurry
The matter of prussian blue material-conductive additive compound and conventional conductive agent Super P, binder polyvinylidene fluoride in material
Amount is than being 80:10:10.
Comparative example 3
With embodiment 1, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
By manganese chloride (MnCl2·4H2O it) is dissolved in deionized water, forms solution one；Carbon nanotube is dispersed in
In deionized water, and sodium ferrocyanide (Na is added4Fe(CN)6·10H2O), solution two is formed；Solution one is slowly added dropwise to molten
It is reacted in liquid two, collects gained precipitating after reaction, add by washing, being drying to obtain prussian blue material-conductive
Add agent compound Na2MnFe(CN)6Carbon nanotube, wherein prussian blue material Na2MnFe(CN)6Partial size D50 be 1 μm,
The content of conductive additive carbon nanotube is the 0.05% of compound gross mass.
By the above-mentioned prussian blue material-conductive additive compound being prepared and conventional conductive agent Super P, glue
Tie agent polyvinylidene fluoride is that 80:10:10 is dissolved in solvent N-methyl pyrilidone in mass ratio, is thoroughly mixed uniformly
Afterwards, anode sizing agent is obtained；Then anode sizing agent is evenly applied on plus plate current-collecting body aluminium foil, later by drying, being cold-pressed, divide
Item obtains positive plate.
Comparative example 4
With embodiment 1, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
By manganese chloride (MnCl2·4H2O it) is dissolved in deionized water, forms solution one；By sodium ferrocyanide (Na4Fe
(CN)6·10H2O it) is dispersed in deionized water, forms solution two；Solution one is slowly added dropwise into solution two and is carried out instead
It answers, gained precipitating is collected after reaction, by washing, being drying to obtain prussian blue material Na2MnFe(CN)6, wherein it is general
Shandong scholar's indigo plant class material Na2MnFe(CN)6Partial size D50 be 1 μm.
By the above-mentioned prussian blue material being prepared and conventional conductive agent Super P, binder polyvinylidene fluoride
It is dissolved in solvent N-methyl pyrilidone for 80:10:10 in mass ratio, after being thoroughly mixed uniformly, obtains anode sizing agent；So
Anode sizing agent is evenly applied on plus plate current-collecting body aluminium foil afterwards, obtains positive plate by drying, cold pressing, slitting later.
Comparative example 5
With embodiment 1, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
By manganese chloride (MnCl2·4H2O it) is dissolved in deionized water, forms solution one；By sodium ferrocyanide (Na4Fe
(CN)6·10H2O it) is dispersed in deionized water, forms solution two；Solution one is slowly added dropwise into solution two and is carried out instead
It answers, gained precipitating is collected after reaction, by washing, being drying to obtain prussian blue material Na2MnFe(CN)6, wherein it is general
Shandong scholar's indigo plant class material Na2MnFe(CN)6Partial size D50 be 1 μm.
By the above-mentioned prussian blue material being prepared and conventional conductive agent Super P, binder polyvinylidene fluoride
It is dissolved in solvent N-methyl pyrilidone for 70:20:10 in mass ratio, after being thoroughly mixed uniformly, obtains anode sizing agent；So
Anode sizing agent is evenly applied on plus plate current-collecting body aluminium foil afterwards, obtains positive plate by drying, cold pressing, slitting later.
Comparative example 6
With embodiment 1, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
By manganese chloride (MnCl2·4H2O it) is dissolved in deionized water, forms solution one；Carbon nanotube is dispersed in
In deionized water, and sodium ferrocyanide (Na is added4Fe(CN)6·10H2O), solution two is formed；Solution one is slowly added dropwise to molten
It is reacted in liquid two, collects gained precipitating after reaction, add by washing, being drying to obtain prussian blue material-conductive
Add agent compound Na2MnFe(CN)6Carbon nanotube, wherein prussian blue material Na2MnFe(CN)6Partial size D50 be 1 μm,
The content of conductive additive carbon nanotube is the 5% of compound gross mass.
By the above-mentioned prussian blue material-conductive additive compound being prepared and binder polyvinylidene fluoride by
Mass ratio is that 90:10 is dissolved in solvent N-methyl pyrilidone, after being thoroughly mixed uniformly, obtains anode sizing agent；Then will
Anode sizing agent is evenly applied on plus plate current-collecting body aluminium foil, obtains positive plate by drying, cold pressing, slitting later.
Comparative example 7
With embodiment 1, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
By manganese chloride (MnCl2·4H2O it) is dissolved in deionized water, forms solution one；Carbon nanotube is dispersed in
In deionized water, and sodium ferrocyanide (Na is added4Fe(CN)6·10H2O), solution two is formed；Solution one is slowly added dropwise to molten
It is reacted in liquid two, collects gained precipitating after reaction, add by washing, being drying to obtain prussian blue material-conductive
Add agent compound Na2MnFe(CN)6Carbon nanotube, wherein prussian blue material Na2MnFe(CN)6Partial size D50 be 1 μm,
The content of conductive additive carbon nanotube is the 25% of compound gross mass.
By the above-mentioned prussian blue material-conductive additive compound being prepared and binder polyvinylidene fluoride by
Mass ratio is that 90:10 is dissolved in solvent N-methyl pyrilidone, after being thoroughly mixed uniformly, obtains anode sizing agent；Then will
Anode sizing agent is evenly applied on plus plate current-collecting body aluminium foil, obtains positive plate by drying, cold pressing, slitting later.
Comparative example 8
With embodiment 2, difference is the preparation process of sodium-ion battery,
(1) preparation of positive plate
Prussian blue material-conductive additive compound, conventional conductive agent Super P, binder are poly- in anode sizing agent
The mass ratio of vinylidene fluoride is 87:3:10.
The test process of sodium-ion battery will be illustrated next.
(1) resistivity measurement of positive diaphragm
The positive plate of embodiment 1-22 and comparative example 1-8 are cut into the square of 10cm × 10cm size, use diaphragm electricity
Hinder tester (single-point method, test area 153.94mm2) resistance of positive diaphragm is measured, every group takes 4 positive plate samples, each
It is averaged after the resistance value of 10 points of sample test, as the resistance value R of the group anode diaphragm, is then counted according to ρ=RS/L
Calculate the resistivity of positive diaphragm, wherein S is the area of positive diaphragm, and L is the thickness of positive diaphragm.
(2) the cycle performance test of sodium-ion battery
At 25 DEG C, by the sodium-ion battery of embodiment 1-22 and comparative example 1-8 with 0.5C multiplying power constant-current charge to voltage
For 4.0V, it is later 0.2C with 4.0V constant-voltage charge to electric current, stands 5min later, is with 0.5C multiplying power constant-current discharge to voltage
1.9V, then 5min is stood, this is a cycle charge discharge electric process, this discharge capacity is denoted as sodium-ion battery the 1st time circulation
Discharge capacity, the as initial capacity of sodium-ion battery.Sodium-ion battery is carried out to 60 cycle charge discharges according to the method described above
Electrical testing, detection obtain the discharge capacity of the 60th circulation.
25 DEG C of sodium-ion battery circulation 60 times after capacity retention ratio (%)=60th time circulation discharge capacity/1st time
Discharge capacity × 100% of circulation.
(3) the high rate performance test of sodium-ion battery
At room temperature, by sodium-ion battery with the multiplying power constant-current charge of 2C to 4.0V, then with the multiplying power constant current of same size
It is discharged to 1.9V, test obtains sodium-ion battery 2C multiplying power discharging capacity.Every group is tested 4 sodium-ion batteries, is averaged.
The parameter and the performance test results of table 1 embodiment 1-22 and comparative example 1-8
It analyzes from the data of table 1 it is found that cathode film sheet resistivity is to the high rate performance of sodium-ion battery, initial capacity and follows
Ring performance has significant impact.Comparative example 4 is only using prussian blue material as positive electrode active materials, although preparing in slurry
When joined wide variety of conventional conductive agent, but the resistivity of positive diaphragm is still larger, is unfavorable for the capacity hair of prussian blue material
It waves, the cycle performance of sodium-ion battery is also poor.Comparative example 5 further increases conventional conductive agent on the basis of comparative example 4
Content, although the resistivity of positive diaphragm reduces, due to prussian blue material itself conduction and lead ionic
Can be poor, the content increase of conventional conductive agent can not fundamentally improve electronics and ion in positive diaphragm in anode sizing agent
Diffusion and transmission, and then can not still be effectively improved the chemical property of sodium-ion battery.Comparative example 6 and comparative example 7 only exist
Prussian blue material surface coats a large amount of conductive additives, is not added conventional conductive agent when preparing anode sizing agent, sodium from
The high rate performance and cycle performance of sub- battery are poor, the reason is that, on the one hand preparation process is limited to, even if preparing compound
When used a large amount of conductive additive, due to the strong absorbency of conductive additive, can not be formed in a solvent evenly dispersed
Mobile phase, can not accomplish that conductive additive is made to be uniformly coated on prussian blue material in situ during synthesising complex
Material particle surface is unable to reach mixed uniformly effect, thus conduction of prussian blue material and lead it is ionic cannot
It is improved；On the other hand since the adhesive substance without electric conductivity to be added when preparing anode sizing agent,
It will increase the interface resistance of positive diaphragm and plus plate current-collecting body when being prepared into positive plate, these are all to hinder electronics and ion motion
Factor, therefore only still can not be effectively improved prussian blue material in prussian blue material surface coated with conductive additive
Expect between particle and the diffusion and transmission of positive diaphragm and plus plate current-collecting body interface electronics and ion, sodium-ion battery it is whole
Body effect is still very poor.
In embodiment 1-22, use prussian blue material-conductive additive compound as positive electrode active materials,
In charge and discharge process, when electronics and ion be diffused into surface inside prussian blue material granule, passes from a particle surface
It is defeated to adjacent particle surface and during opposite, conductive additive there are the diffusions and transmission of electron and ion
Good channel is provided, therefore conduction of positive diaphragm can be significantly improved and lead ionic, the resistance of the positive diaphragm of reduction
Rate ensure that electronics and ion reversibly can spread and transmit relatively in charge and discharge process, to keep sodium-ion battery simultaneous
Care for preferable high rate performance, higher initial capacity and good cycle performance.
In embodiment 1-22, it is to be understood that conductive additive is different with the type of conventional conductive agent, to sodium ion
The performance improvement effect of battery is also different.Wherein conducting polymer is better than the effect that sodium-ion battery cycle performance improves inorganic
Conductive agent, reason may is that the backbone of conducting polymer can connect more prussian blue material granules, thus
The long range electric conductivity of prussian blue material can more be effectively improved；On the other hand, conducting polymer and prussian blue material
Long-range reticular structure between material particle also functions to the effect of stable prussian blue material structure to a certain extent, it is suppressed that
Issuable volume and structure change in charge and discharge process are advantageous to the cycle performance for improving sodium-ion battery.And it inorganic leads
Electric agent is better than conducting polymer to the improvement of sodium-ion battery high rate performance, and possible reason is conducting polymer itself
Electric conductivity it is slightly poor (electric conductivity and conventional semiconductor close), during sodium-ion battery high rate charge-discharge, electronics and from
Son, which not can be carried out, timely to be spread and transmits.It is therefore preferred that conductive additive includes simultaneously inorganic conductive agent and conducting polymer
Object can not only play the long-range electric conductivity of conducting polymer in this way, but also can make electricity by the excellent electric conductivity of inorganic conductive agent
Son and ion are timely spread and are transmitted.
Meanwhile influence of the dosage of conductive additive to cathode film sheet resistivity is also easier to understand.Conductive additive
Content it is less, then conductive additive cannot be uniformly coated on prussian blue material granule surface, thus cannot be effectively
It improves conduction of positive diaphragm and leads ionic.Conductive additive, such as the content of conducting polymer are more, synthesize in situ
During prussian blue material-conductive additive compound, it may be affected general due to the presence of excessive conducting polymer
The crystal growth of Shandong scholar's indigo plant class material, causes prussian blue material crystal structure and chemical composition existing defects, to influence
The capacity of prussian blue material plays, and leads to the initial capacity reduction of sodium-ion battery.It can in conjunction with the test result of comparative example 1
Know, although the resistivity of positive diaphragm is lower, due to coating an excess amount of conducting polymer in prussian blue material surface
Object affects the crystal growth of prussian blue material, causes crystal structure and chemical composition existing defects, affects Prussia
The capacity of blue class material plays.And conductive additive, such as the content of inorganic conductive agent are more, these in synthesis are inorganic in situ
Conductive agent leads to the feasibility for preparing material due to can not usually form evenly dispersed mobile phase with stronger imbibition effect
It is poor with practicability.
In embodiment 13-17, the partial size of prussian blue material granule has certain influence to cathode film sheet resistivity.It is general
The partial size of Shandong scholar's indigo plant class material granule is bigger, and the transmission path of electronics and ion inside single particle is longer, thus anode
Diaphragm conduction son and lead it is ionic poorer.But in comparison, influence of the partial size to sodium-ion battery performance is still wanted
Contain less than conventional conductive agent in conductive additive content in prussian blue material-conductive additive compound and positive diaphragm
Measuring bring influences.
In conclusion either conductive additive or conventional conductive agent, content should control in a certain range,
Guarantee on the one hand to achieve the effect that improve sodium-ion battery chemical property, on the other hand, and will not be because of excessive conduction
The use of additive or conventional conductive agent destroys the crystal and chemical structure of prussian blue material, influences electronics, ion
Normal diffusion and transmission channel, reduce the content of active sodium ion, will not reduce prussian blue material in positive diaphragm
Load capacity avoids the compacted density for influencing positive diaphragm, loses the energy density of sodium-ion battery.Therefore, in practical applications,
The type and dosage of suitable conductive additive, conventional conductive agent are selected as needed.
Claims (10)
1. a kind of positive plate, comprising:
Plus plate current-collecting body；And
Positive diaphragm is set on the plus plate current-collecting body；
It is characterized in that,
The anode diaphragm includes positive electrode active materials；
The positive electrode active materials include prussian blue material-conductive additive compound；
The molecular formula of the prussian blue material is AxMy[M′(CN)6]z, wherein A is alkali metal cation, alkaline-earth metal sun
One or more of ion, M are transition metal, and M ' is transition metal, 0 < x≤2,0 < y≤1,0 z≤1 <；
The resistivity of the anode diaphragm is less than or equal to 400 Ω cm, the preferably 15 Ω cm of Ω cm~400, further excellent
It is selected as 30 Ω of Ω cm~200 cm.
2. positive plate according to claim 1, which is characterized in that the conductive additive is selected from inorganic conductive agent, conduction
One or more of polymer, it is preferable that the conductive additive is the mixture of inorganic conductive agent and conducting polymer.
3. positive plate according to claim 2, which is characterized in that in the composite:
The content of the inorganic conductive agent is the 0.1%~5% of the compound gross mass, preferably 0.5%~3%；
The content of the conducting polymer is the 0.1%~15% of the compound gross mass, preferably 1%~3%.
4. positive plate according to claim 2, which is characterized in that
The inorganic conductive agent be selected from acetylene black, conductive black, Ketjen black, carbon nanotube, carbon fiber, carbon nanocoils, graphene,
One or more of carbon nanobelts, electrically conductive graphite；
The conducting polymer is selected from one or more of polypyrrole, polyaniline, polythiophene, polyphenylene sulfide and its derivative.
5. positive plate according to claim 1, which is characterized in that the anode diaphragm further includes conventional conductive agent.
6. positive plate according to claim 5, which is characterized in that the content of the conventional conductive agent be more than or equal to it is described just
The 5% of pole diaphragm gross mass, preferably 5%~20%.
7. positive plate according to claim 1, which is characterized in that the partial size D50 of the prussian blue material is 0.5 μm
~5 μm.
8. positive plate according to claim 1, which is characterized in that the prussian blue material is cube phase structure or six
Square phase structure.
9. positive plate according to claim 1, which is characterized in that it is described anode diaphragm with a thickness of 10 μm~200 μm, it is excellent
It is selected as 60 μm~120 μm.
10. a kind of electrochemical cell, which is characterized in that including positive plate of any of claims 1-9.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110707319A (en) * | 2019-09-27 | 2020-01-17 | 上海应用技术大学 | Three-dimensional structured graphene-based iron oxide composite material and preparation and application thereof |
| CN112259730A (en) * | 2020-12-08 | 2021-01-22 | 江苏时代新能源科技有限公司 | Prussian blue transition metal cyanide, preparation method thereof, and related positive electrode plate, secondary battery, battery pack and device |
| CN113346063A (en) * | 2021-06-01 | 2021-09-03 | 上海电力大学 | Water-based zinc ion battery positive electrode material and preparation method thereof |
| CN114023938A (en) * | 2021-11-04 | 2022-02-08 | 山东零壹肆先进材料有限公司 | Positive electrode material and preparation method and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101378124A (en) * | 2007-08-28 | 2009-03-04 | 德固赛（中国）投资有限公司 | Secondary battery and anode active substance |
| CN102522553A (en) * | 2011-12-31 | 2012-06-27 | 武汉大学 | Sodium ion battery positive material |
| US20130266861A1 (en) * | 2012-03-28 | 2013-10-10 | Sharp Laboratories Of America, Inc. | Metal-Doped Transition Metal Hexacyanoferrate (TMHCF) Battery Electrode |
| CN103456936A (en) * | 2012-05-31 | 2013-12-18 | 中国科学院物理研究所 | Sodium ion secondary battery, and layered titanate active substance, electrode material, anode and cathode adopted by the sodium ion secondary battery, and preparation method of the layered titanate active substance |
| US20170092937A1 (en) * | 2015-09-30 | 2017-03-30 | Sumitomo Osaka Cement Co., Ltd. | Electrode material for lithium-ion rechargeable battery, method for manufacturing electrode material for lithium-ion rechargeable battery, electrode for lithium-ion rechargeable battery, and lithium-ion rechargeable battery |
| WO2017099137A1 (en) * | 2015-12-07 | 2017-06-15 | 国立研究開発法人産業技術総合研究所 | Positive electrode active material for potassium ion secondary cell |
| CN106910888A (en) * | 2017-01-14 | 2017-06-30 | 复旦大学 | A kind of potassium/Prussian blue secondary cell |
| CN106960956A (en) * | 2017-04-01 | 2017-07-18 | 上海中聚佳华电池科技有限公司 | Modified Prussian blue material, sodium-ion battery positive plate and preparation method |
| CN107226475A (en) * | 2017-06-08 | 2017-10-03 | 西安交通大学 | A kind of kalium ion battery positive electrode and preparation method thereof and kalium ion battery |
| CN107369846A (en) * | 2017-07-14 | 2017-11-21 | 北京理工大学 | Electrode slice and preparation method thereof and aluminium ion battery |
| CN107394152A (en) * | 2017-07-17 | 2017-11-24 | 深圳市贝特瑞纳米科技有限公司 | The spherical composite of the high graphene-based LiFePO4 of conductance, its preparation method and include its lithium ion battery |
-
2017
- 2017-12-12 CN CN201711318082.4A patent/CN109920979B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101378124A (en) * | 2007-08-28 | 2009-03-04 | 德固赛（中国）投资有限公司 | Secondary battery and anode active substance |
| CN102522553A (en) * | 2011-12-31 | 2012-06-27 | 武汉大学 | Sodium ion battery positive material |
| US20130266861A1 (en) * | 2012-03-28 | 2013-10-10 | Sharp Laboratories Of America, Inc. | Metal-Doped Transition Metal Hexacyanoferrate (TMHCF) Battery Electrode |
| CN103456936A (en) * | 2012-05-31 | 2013-12-18 | 中国科学院物理研究所 | Sodium ion secondary battery, and layered titanate active substance, electrode material, anode and cathode adopted by the sodium ion secondary battery, and preparation method of the layered titanate active substance |
| US20170092937A1 (en) * | 2015-09-30 | 2017-03-30 | Sumitomo Osaka Cement Co., Ltd. | Electrode material for lithium-ion rechargeable battery, method for manufacturing electrode material for lithium-ion rechargeable battery, electrode for lithium-ion rechargeable battery, and lithium-ion rechargeable battery |
| WO2017099137A1 (en) * | 2015-12-07 | 2017-06-15 | 国立研究開発法人産業技術総合研究所 | Positive electrode active material for potassium ion secondary cell |
| CN106910888A (en) * | 2017-01-14 | 2017-06-30 | 复旦大学 | A kind of potassium/Prussian blue secondary cell |
| CN106960956A (en) * | 2017-04-01 | 2017-07-18 | 上海中聚佳华电池科技有限公司 | Modified Prussian blue material, sodium-ion battery positive plate and preparation method |
| CN107226475A (en) * | 2017-06-08 | 2017-10-03 | 西安交通大学 | A kind of kalium ion battery positive electrode and preparation method thereof and kalium ion battery |
| CN107369846A (en) * | 2017-07-14 | 2017-11-21 | 北京理工大学 | Electrode slice and preparation method thereof and aluminium ion battery |
| CN107394152A (en) * | 2017-07-17 | 2017-11-24 | 深圳市贝特瑞纳米科技有限公司 | The spherical composite of the high graphene-based LiFePO4 of conductance, its preparation method and include its lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 唐阳: ""普鲁士蓝复合材料的制备及其储钠性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110707319A (en) * | 2019-09-27 | 2020-01-17 | 上海应用技术大学 | Three-dimensional structured graphene-based iron oxide composite material and preparation and application thereof |
| CN110707319B (en) * | 2019-09-27 | 2021-09-28 | 上海应用技术大学 | Three-dimensional structured graphene-based iron oxide composite material and preparation and application thereof |
| CN112259730A (en) * | 2020-12-08 | 2021-01-22 | 江苏时代新能源科技有限公司 | Prussian blue transition metal cyanide, preparation method thereof, and related positive electrode plate, secondary battery, battery pack and device |
| WO2022121570A1 (en) * | 2020-12-08 | 2022-06-16 | 宁德时代新能源科技股份有限公司 | Prussian blue transition metal cyanide, preparation method therefor, and positive electrode pole piece, secondary battery, battery module, battery pack, and apparatus related to prussian blue transition metal cyanide |
| CN113346063A (en) * | 2021-06-01 | 2021-09-03 | 上海电力大学 | Water-based zinc ion battery positive electrode material and preparation method thereof |
| CN114023938A (en) * | 2021-11-04 | 2022-02-08 | 山东零壹肆先进材料有限公司 | Positive electrode material and preparation method and application thereof |
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