CN109119610A - A kind of alkaline aqueous solution sodium-ion battery - Google Patents
A kind of alkaline aqueous solution sodium-ion battery Download PDFInfo
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- CN109119610A CN109119610A CN201810948902.6A CN201810948902A CN109119610A CN 109119610 A CN109119610 A CN 109119610A CN 201810948902 A CN201810948902 A CN 201810948902A CN 109119610 A CN109119610 A CN 109119610A
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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
- H01M10/24—Alkaline accumulators
- H01M10/28—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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
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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
It is disclosed herein and has invented a kind of alkaline aqueous solution sodium-ion battery and preparation method thereof, be primarily characterized in that, the positive electrode used is NaxMnyNzO2, N is doped chemical, can be one or more of metallic elements such as Ca, Ti, V, Cr, Mn, Fe ﹑ Co, Ni, Cu, Zn, Al ﹑ Zr, Ru.Negative electrode material be active carbon, titanium phosphate sodium etc. can stabilized aqueous solution deintercalation sodium ion electrode material and can be stable in alkaline aqueous solution zinc electrode.Electrolyte is alkaline aqueous solution.The positive electrode that the present invention uses first all charging capacitys with higher, and take into account the features such as raw material is cheap, preparation process is simple.Alkaline electrolyte has higher conductivity and stability compared with neutral electrolyte, reduces the requirement to collector and other metal fittings and improves range of choice, has good Commercial Prospect.
Description
Technical field
The invention belongs to secondary cell field more particularly to a kind of alkaline aqueous solution sodium-ion batteries.
Background technique
People to petroleum, matchmaker, natural gas, etc. consuming excessively for non-renewable resources cause energy and environmental problem increasingly tight
It is imperative to develop the renewable energy such as wind energy, solar energy, tide energy for weight, however electrochemical energy storage becomes limitation renewable energy
One of the key technology of source large-scale application.Simultaneously with advances in technology, expanding economy and living standards of the people mention
Height, to electrochemical energy storage device, more stringent requirements are proposed in the fields such as national defence, traffic, portable equipment.Search out a kind of high-energy
Density, high power density, the electrochemical appliance that safety is good, cheap have become a kind of extremely urgent thing.Lithium ion is made
For a kind of secondary cell, successfully applied in the fields such as mancarried electronic aid and power vehicle, however due to
The scarcity of lithium resource reserves is unevenly distributed and adopts the limitation of lithium technology, and the cost of lithium ion battery gradually rises, and makes lithium ion
Battery loses the advantage applied in terms of extensive energy storage.Replacer of the sodium-ion battery as lithium ion battery, there is phase
Same energy storage mechnism, and rich reserves, exploitation are simply, there is very big application prospect in terms of extensive energy storage.
For water-soluble battery compared with organic system battery, electrolyte is aqueous solution, is had cheap, nontoxic, environmentally friendly.No
It will appear the serious safety problem as organic system.However the water-soluble solution battery of existing sodium ion, electrolyte are mostly neutrality
Aqueous solution, such as aqueous sodium persulfate solution and sodium nitrate aqueous solution.When slight liberation of hydrogen analysis oxygen occurs, the pH of electrolyte is easy to send out
Raw larger change, corrodes collector and electrode material, leads to battery actual effect, while to prevent from corroding, collector and shell etc. are golden
Belong to accessory and mostly use some more expensive materials, this considerably increases costs.However alkaline aqueous solution sodium-ion battery is using alkalinity
The oxygen evolution potential of battery not only can be improved as electrolyte in aqueous solution, and stable alkaline environment can also prevent and slow down collection
The corrosion of the metal fittings such as fluid, shell, therefore cost can be reduced using cheap materials such as nickel foam, stainless steels.
Summary of the invention
Technical problem to be solved by the present invention lies in provide a kind of alkaline aqueous solution sodium-ion battery, relatively existing sodium
Deionized water solution battery can not only reduce cost, with more excellent capacitance and cyclical stability.
Technical solution of the present invention can be realized by following technical measures:
A kind of alkaline aqueous solution sodium-ion battery, comprising:
Anode: it is formed by being adhered on collector after positive active material, binder, conductive agent mixing, the anode is living
Property substance be NaxMnyNzO2, wherein 0.44≤x≤0.55,0≤y≤1, z=1-y, N Ca, Ti, V, Cr, Mn, Fe ﹑ Co,
One or more of Ni, Cu, Zn, Al ﹑ Zr, Ru metallic element；
Cathode；
Diaphragm；
Electrolyte: solute is the alkaline aqueous solution of sodium salt；
Shell.
Preferably, the positive active material is NaxMnyNzO2, wherein 0.44≤x≤0.55,0≤z≤0.2, z=1-
y。
Preferably, binder is polytetrafluoroethylene (PTFE), Kynoar, polyvinyl alcohol, sodium carboxymethylcellulose, styrene-butadiene latex
One of or it is a variety of；Conductive agent is one of graphite, carbon black, iron powder, manganese powder, copper powder, aluminium powder or a variety of；Collector is
Titanium, copper, aluminium, stainless steel, nickel paillon or net.
Preferably, the enclosure material is selected from glass, metal, inorganic matter ceramics, plastics, rubber, resin or metal and modeling
The composite material of material, rubber and resin composition；The form of the battery is button, column or Soft Roll.
Preferably, the negative electrode material is obtained by being adhered on collector after negative electrode active material, binder, conductive agent mixing
It arrives, the negative electrode active material is can be in stabilized aqueous solution adsorption desorption, the electrode material of deintercalation sodium ion, such as active carbon, phosphoric acid
Titanium sodium, the binder are polytetrafluoroethylene (PTFE), Kynoar, polyvinyl alcohol, sodium carboxymethylcellulose, one in styrene-butadiene latex
Kind is a variety of；Conductive agent is one of graphite, carbon black, iron powder, manganese powder, copper powder, aluminium powder or a variety of；Collector be titanium, copper,
Aluminium, stainless steel, nickel paillon or net.
Preferably, the negative electrode material can also be zinc metal sheet or zinc powder.
Preferably, the diaphragm is selected from non-woven fabrics, glass fibre, porous PP/PE diaphragm, PVDF or PTFE film.
Preferably, the electrolyte solute sodium salt is sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium phosphate, one hydrogen of phosphoric acid
The basic salts such as sodium, sodium sulfite it is one or more.
Preferably, additive is added in the electrolyte solution, the additive includes zinc powder, oxide powder and zinc etc..
Preferably, the molar concentration of the electrolyte solution is 0.5~10.
Preferably, the positive active material NaxMnyNzO2The preparation method is as follows:
(1) Na, Mn are pressed、N molar ratio is that x:y:z weighs sodium acetate, four water manganese acetates and the salt containing N, and mixing is dissolved in anhydrous
In the mixing liquid of second alcohol and water, 50~90 DEG C of heating stirring to salt are completely dissolved, and phenol is then added and formalin continues
Heating stirring makes mixed solution become gel-like solid；
(2) gained gelatinous solid is dried in vacuo to 8~15h at 50~100 DEG C；
(3) solid after drying is fully ground, 700~1000 DEG C of 8~15h of calcining, obtain in air atmosphere
NaxMnyNzO2Positive active material.
Compared with prior art, the invention has the following beneficial effects:
Gained alkaline aqueous solution sodium-ion battery charging capacity with higher of the invention, and take into account that raw material is cheap, system
The features such as simple for process.Alkaline electrolyte has higher conductivity and stability compared with neutral electrolyte, reduces to collection
The requirement of fluid and other metal fittings simultaneously improves range of choice, has good Commercial Prospect.
Detailed description of the invention
The present invention will be further described with reference to the accompanying drawings, but the embodiment in attached drawing is not constituted to any limit of the invention
System.
Fig. 1 is the charging and discharging curve of battery in comparative example 1；
Fig. 2 is the cycle performance curve of battery in comparative example 1；
Fig. 3 is the charging and discharging curve of battery in comparative example 2；
Fig. 4 is the cycle performance curve of battery in comparative example 2；
Fig. 5 is the charging and discharging curve of battery in embodiment 1；
Fig. 6 is the cycle performance curve of battery in embodiment 1；
Fig. 7 is the charging and discharging curve of battery in embodiment 2；
Fig. 8 is the cycle performance curve of battery in embodiment 2；
Fig. 9 is the charging and discharging curve of battery in embodiment 3；
Figure 10 is the charging and discharging curve of battery in embodiment 4；
Figure 11 is the charging and discharging curve of battery in embodiment 5；
Figure 12 is the charging and discharging curve of battery in embodiment 6.
Specific embodiment
To keep the present invention easier to understand, specific embodiments of the present invention are further illustrated below.
Comparative example 1
This comparative example describes one kind with tunnel type oxide Na0.44MnO2For anode, using active carbon as the neutral water of cathode
Solution sodium-ion battery.
(1) anode portion: Na0.44MnO2Synthesis: weigh sodium acetate and four water manganese acetate raw materials in molar ratio for 0.44: 1
It is dissolved in dehydrated alcohol, 50~90 DEG C of heating stirrings in heat-collecting magnetic stirring device, while deionized water is slowly added dropwise to second
Hydrochlorate is completely dissolved.Then phenol and formalin are added in mixed solution.Continue heating stirring to mixed solution and becomes solidifying
Gelatinous solid.Gelatinous solid is transferred in 50~100 DEG C of vacuum oven, is dried in vacuo 8~15h.Consolidating after drying
Body is fully ground, and is put into the Muffle furnace under air atmosphere, 700~900 DEG C of 8~15h of calcining.
Na0.44MnO2The preparation of electrode: Na0.44MnO2For positive active material, conductive black SP is conductive agent, 60wt%
PTFE emulsion be binder, according to active material: conductive agent: the weight ratio of binder 80: 10: 10 weighs active matter
Matter, conductive agent, binder.First active material and conductive carbon are ground in agate mortar uniformly.Binder is taken to be put in small burning again
In cup, adds a little isopropanol to be demulsified, ground dusty material is then added, sizes mixing, dry under infrared lamp, finally to roller
Film forming is rolled on machine.Diaphragm is put into 100 DEG C of vacuum drying ovens and keeps 6h or more.It is compressed on stainless (steel) wire.
(2) cathode portion: activated carbon electrodes are prepared by rolling embrane method.Active carbon is negative electrode active material, and Ketjen black is conduction
The PTFE emulsion of agent, 60wt% is binder, and according to active material: conductive agent: the weight ratio of binder 70: 20: 10 claims
Take active material, conductive agent, binder.First active material and conductive carbon are ground in agate mortar uniformly.Binder is taken again
It is put in small beaker, adds a little isopropanol to be demulsified, ground dusty material is then added, sizes mixing, dry under infrared lamp,
Film forming is finally rolled on twin rollers.Diaphragm is put into 100 DEG C of vacuum drying ovens and keeps 6h or more.It is compressed on stainless (steel) wire.
(3) electrolyte: electrolyte 1molL-1Aqueous sodium persulfate solution.
Experimental cell is carried out in a U-shaped vial equipped with 10ml electrolyte, and aqueous solution electrolysis is finally assembled into
The sodium-ion battery of liquid.It is tested using constant current charge-discharge mode, charging is 1.65V by voltage, and electric discharge is by voltage
0V.Fig. 1 is the charging and discharging curve of battery in comparative example 1, and current density is 1C (1C=121 MAhs/g), and Fig. 2 is comparative example 1
The cycle performance curve of middle battery, current density 10C.As can be seen that battery discharge specific capacity is under the current density of 1C
45.6 MAhs/g.Under the high current density of 10C, it is 60.2% that 1000 weeks capacity, which keep interest rate,.
Comparative example 2
This comparative example describes one kind with tunnel type oxide Na0.44MnO2For anode, using active carbon as the alkaline water of cathode
Solution sodium-ion battery.
(1) preparation method with comparative example one of anode portion is identical.
(2) cathode portion: activated carbon electrodes are prepared by rolling embrane method.Active carbon is negative electrode active material, and Ketjen black is conduction
The PTFE emulsion of agent, 60wt% is binder, and according to active material: conductive agent: the weight ratio of binder 70: 20: 10 claims
Take active material, conductive agent, binder.First active material and conductive carbon are ground in agate mortar uniformly.Binder is taken again
It is put in small beaker, adds a little isopropanol to be demulsified, ground dusty material is then added, sizes mixing, dry under infrared lamp,
Film forming is finally rolled on twin rollers.Diaphragm is put into 100 DEG C of vacuum drying ovens and keeps 6h or more.It is compressed on stainless (steel) wire.
(3) electrolyte: electrolyte 6molL-1Sodium hydrate aqueous solution.
Experimental cell is carried out in a U-shaped vial equipped with 10ml electrolyte, and aqueous solution electrolysis is finally assembled into
The sodium-ion battery of liquid.It is tested using constant current charge-discharge mode, charging is 1.65V by voltage, and electric discharge is by voltage
0V.Fig. 3 is the charging and discharging curve of battery in comparative example 2, and current density is 1C (1C=121 MAhs/g), and Fig. 4 is comparative example 2
The cycle performance curve of middle battery, current density 10C.As can be seen that battery discharge specific capacity is under the current density of 1C
76.9 MAhs/g, compare Na0.44MnO2The capacity of neutral aqueous solution sodium-ion battery is higher by 30 MAhs/g or so, this benefit
The hydrogen-evolution overpotential of battery can be substantially reduced in alkaline aqueous solution, while inhibiting hydrionic insertion in positive electrode.In the big of 10C
Under current density, possess good cycle performance, it is 65.1% that 1000 weeks capacity, which keep interest rate,.Good performance and it is cheap at
Originally good Commercial Prospect is made it have.
Embodiment 1:
This example describes one kind with tunnel type oxide Na0.5Mn0.9Fe0.1O2For anode, using zinc metal sheet as the alkalinity of cathode
Aqueous solution sodium-ion battery.
(1) anode portion: Na0.5Mn0.9Fe0.1O2Synthesis: sodium acetate, four water second are weighed for 0.5:0.9:0.1 in molar ratio
Sour manganese and ironic citrate are dissolved in dehydrated alcohol, 50~90 DEG C of heating stirrings in heat-collecting magnetic stirring device, while slowly drop
Deionized water to all salt are added to be completely dissolved.Then phenol and formalin are added in mixed solution.Continue heating stirring extremely
The solid that mixed solution becomes gel-like.Gelatinous solid is transferred in 50~100 DEG C of vacuum oven, vacuum drying 8~
15h.Solid after drying is fully ground, and is put into the Muffle furnace under air atmosphere, 700~900 DEG C of 8~15h of calcining.
Na0.5Mn0.9Fe0.1O2The preparation of electrode: Na0.5Mn0.9Fe0.1O2For positive active material, conductive black SP is conduction
The PTFE emulsion of agent, 60wt% is binder, and according to active material: conductive agent: the weight ratio of binder 80: 10: 10 claims
Take active material, conductive agent, binder.First active material and conductive carbon are ground in agate mortar uniformly.Binder is taken again
It is put in small beaker, adds a little isopropanol to be demulsified, ground dusty material is then added, sizes mixing, dry under infrared lamp,
Film forming is finally rolled on twin rollers.Diaphragm is put into 100 DEG C of vacuum drying ovens and keeps 6h or more.It is compressed on stainless (steel) wire.
(2) cathode portion: zinc metal sheet takes the zinc metal sheet of 0.1~1mm of thickness, is polished smooth with sand paper as cathode, and ethyl alcohol rinses
Afterwards, it dries.Suitable shape is cut into scissors.
(3) electrolyte: electrolyte 6molL-1Sodium hydrate aqueous solution.
Experimental cell is carried out in a U-shaped vial equipped with 10ml electrolyte, and aqueous solution electrolysis is finally assembled into
The sodium-ion battery of liquid.It is tested using constant current charge-discharge mode, charging is 2.0V by voltage, and electric discharge is by voltage
1.15V.Fig. 5 is the charging and discharging curve of battery in embodiment 1, and current density is 1C (1C=121 MAhs/g), and Fig. 6 is to implement
The cycle performance curve of battery, current density 10C in example 1.As can be seen that under the current density of 1C, battery discharge specific volume
Amount is 74.8 MAhs/g, compares Na0.44MnO2The capacity of neutral aqueous solution sodium-ion battery is higher by 30 MAhs/g or so, this
The hydrogen-evolution overpotential of battery can be substantially reduced by having benefited from alkaline aqueous solution, while inhibit hydrionic insertion in positive electrode.In 10C
High current density under, possess good cycle performance, it is 74.8% that 1000 weeks capacity, which keep interest rate, this has benefited from ion doping
Improve the structural stability of crystal.Good performance and cheap cost make it have good Commercial Prospect.
Embodiment 2:
This example describes one kind with tunnel type oxide Na0.5Mn0.9Al0.1O2For anode, using active carbon as the alkali of cathode
Property aqueous solution sodium-ion battery.
(1) anode portion: Na0.5Mn0.9Al0.1O2: sodium acetate, four water manganese acetates are weighed in molar ratio for 0.5:0.9:0.1
Be dissolved in dehydrated alcohol with aluminum nitrate, 50~90 DEG C of heating stirrings in heat-collecting magnetic stirring device, at the same be slowly added dropwise from
Sub- water to all salt are completely dissolved.Then phenol and formalin are added in mixed solution.It is molten to mixing to continue heating stirring
The solid that liquid becomes gel-like.Gelatinous solid is transferred in 50~100 DEG C of vacuum oven, is dried in vacuo 8~15h.It is dry
Solid after dry is fully ground, and is put into the Muffle furnace under air atmosphere, 700~900 DEG C of 8~15h of calcining.
Na0.5Mn0.9Al0.1O2The preparation of electrode: Na0.5Mn0.9Al0.1O2For positive active material, conductive black SP is conduction
The PTFE emulsion of agent, 60wt% is binder, and according to active material: conductive agent: the weight ratio of binder 80: 10: 10 claims
Take active material, conductive agent, binder.First active material and conductive carbon are ground in agate mortar uniformly.Binder is taken again
It is put in small beaker, adds a little isopropanol to be demulsified, ground dusty material is then added, sizes mixing, dry under infrared lamp,
Film forming is finally rolled on twin rollers.Diaphragm is put into 100 DEG C of vacuum drying ovens and keeps 6h or more.It is compressed in nickel foam.
(2) cathode portion: activated carbon electrodes are prepared by rolling embrane method.Active carbon is negative electrode active material, and Ketjen black is conduction
The PTFE emulsion of agent, 60wt% is binder, and according to active material: conductive agent: the weight ratio of binder 70: 20: 10 claims
Take active material, conductive agent, binder.First active material and conductive carbon are ground in agate mortar uniformly.Binder is taken again
It is put in small beaker, adds a little isopropanol to be demulsified, ground dusty material is then added, sizes mixing, dry under infrared lamp,
Film forming is finally rolled on twin rollers.Diaphragm is put into 100 DEG C of vacuum drying ovens and keeps 6h or more.It is compressed on stainless (steel) wire.
(3) electrolyte: electrolyte 6molL-1Sodium hydrate aqueous solution.
Experimental cell is carried out in a U-shaped vial equipped with 10ml electrolyte, and aqueous solution electrolysis is finally assembled into
The sodium-ion battery of liquid.It is tested using constant current charge-discharge mode, charging is 1.65V by voltage, and electric discharge is by voltage
0V.Fig. 7 is the charging and discharging curve of battery in embodiment 2, and current density is 1C (1C=121 MAhs/g), and Fig. 8 is embodiment 2
The cycle performance curve of middle battery, current density 10C.As can be seen that battery discharge specific capacity is under the current density of 1C
72.2 MAhs/g, also compare Na0.44MnO2The capacity of neutral aqueous solution sodium-ion battery is higher by 30 MAhs/g or so, this is obtained
The hydrogen-evolution overpotential of battery can be substantially reduced beneficial to alkaline aqueous solution, while inhibiting hydrionic insertion in positive electrode.10C's
Under high current density, possess good cycle performance, it is 70% that 2000 weeks capacity, which keep interest rate, this has benefited from ion doping promotion
The structural stability of crystal.Good performance and cheap cost make it have good Commercial Prospect.
Embodiment 3:
This example describes one kind with tunnel type oxide Na0.5Mn0.9Co0.1O2For anode, using zinc metal sheet as the alkalinity of cathode
Aqueous solution sodium-ion battery.
(1) anode portion: Na0.5Mn0.9Co0.1O2Synthesis: weigh sodium acetate, four water in molar ratio for 0.5:0.9:0.1
Manganese acetate and cobalt nitrate are dissolved in dehydrated alcohol, 50~90 DEG C of heating stirrings in heat-collecting magnetic stirring device, while slowly drop
Deionized water to all salt are added to be completely dissolved.Then phenol and formalin are added in mixed solution.Continue heating stirring extremely
The solid that mixed solution becomes gel-like.Gelatinous solid is transferred in 50~100 DEG C of vacuum oven, vacuum drying 8~
15h.Solid after drying is fully ground, and is put into the Muffle furnace under air atmosphere, 700~900 DEG C of 8~15h of calcining.
Na0.5Mn0.9Co0.1O2The preparation of electrode: Na0.5Mn0.9Co0.1O2For positive active material, conductive black SP is conduction
The PTFE emulsion of agent, 60wt% is binder, and according to active material: conductive agent: the weight ratio of binder 80: 10: 10 claims
Take active material, conductive agent, binder.First active material and conductive carbon are ground in agate mortar uniformly.Binder is taken again
It is put in small beaker, adds a little isopropanol to be demulsified, ground dusty material is then added, sizes mixing, dry under infrared lamp,
Film forming is finally rolled on twin rollers.Diaphragm is put into 100 DEG C of vacuum drying ovens and keeps 6h or more.It is compressed on stainless (steel) wire.
(2) cathode portion: zinc metal sheet takes the zinc metal sheet of 0.1~1mm of thickness, is polished smooth with sand paper as cathode, and ethyl alcohol rinses
Afterwards, it dries.Suitable shape is cut into scissors.
(3) electrolyte: electrolyte 6molL-1Sodium hydrate aqueous solution.
Experimental cell is carried out in a U-shaped vial equipped with 10ml electrolyte, and aqueous solution electrolysis is finally assembled into
The sodium-ion battery of liquid.It is tested using constant current charge-discharge mode, charging is 2.0V by voltage, and electric discharge is by voltage
1.15V.Fig. 9 is the charging and discharging curve of battery in embodiment 3, and current density is 1C (1C=121 MAhs/g).As can be seen that
Under the current density of 1C, battery discharge specific capacity is 78.4 MAhs/g, also compares Na0.44MnO2Neutral aqueous solution sodium ion electricity
The capacity in pond is higher by 30 MAhs/g or so, this, which has benefited from alkaline aqueous solution, can substantially reduce the hydrogen-evolution overpotential of battery, presses down simultaneously
Hydrionic insertion in positive electrode processed.Good performance and cheap cost make it have good Commercial Prospect.
Embodiment 4:
This example describes one kind with tunnel type oxide Na0.5Mn0.9V0.1O2For anode, using active carbon as the alkali of cathode
Property aqueous solution sodium-ion battery.
(1) anode portion: Na0.5Mn0.9V0.1O2: sodium acetate, four water manganese acetates are weighed in molar ratio for 0.5:0.9:0.1
It is dissolved in dehydrated alcohol, 50~90 DEG C of heating stirrings in heat-collecting magnetic stirring device, while being slowly added dropwise with vanadyl oxalate
Ionized water to all salt are completely dissolved.Then phenol and formalin are added in mixed solution.Continue heating stirring to mixing
The solid that solution becomes gel-like.Gelatinous solid is transferred in 50~100 DEG C of vacuum oven, is dried in vacuo 8~15h.
Solid after drying is fully ground, and is put into the Muffle furnace under air atmosphere, 700~900 DEG C of 8~15h of calcining.
Na0.5Mn0.9V0.1O2The preparation of electrode: Na0.5Mn0.9V0.1O2For positive active material, conductive black SP is conduction
The PTFE emulsion of agent, 60wt% is binder, and according to active material: conductive agent: the weight ratio of binder 80: 10: 10 claims
Take active material, conductive agent, binder.First active material and conductive carbon are ground in agate mortar uniformly.Binder is taken again
It is put in small beaker, adds a little isopropanol to be demulsified, ground dusty material is then added, sizes mixing, dry under infrared lamp,
Film forming is finally rolled on twin rollers.Diaphragm is put into 100 DEG C of vacuum drying ovens and keeps 6h or more.It is compressed in nickel foam.
(2) cathode portion: activated carbon electrodes are prepared by rolling embrane method.Active carbon is negative electrode active material, and Ketjen black is conduction
The PTFE emulsion of agent, 60wt% is binder, and according to active material: conductive agent: the weight ratio of binder 70: 20: 10 claims
Take active material, conductive agent, binder.First active material and conductive carbon are ground in agate mortar uniformly.Binder is taken again
It is put in small beaker, adds a little isopropanol to be demulsified, ground dusty material is then added, sizes mixing, dry under infrared lamp,
Film forming is finally rolled on twin rollers.Diaphragm is put into 100 DEG C of vacuum drying ovens and keeps 6h or more.It is compressed on stainless (steel) wire.
(3) electrolyte: electrolyte 6molL-1Sodium hydrate aqueous solution.
Experimental cell is 2032 button cells.It is tested using constant current charge-discharge mode, charging is by voltage
1.65V, electric discharge are 0V by voltage.Figure 10 is the charging and discharging curve of battery in embodiment 4, and current density is 1C (1C=121 milli
Ampere-hour/gram).As can be seen that battery discharge specific capacity is 76.9 MAhs/g under the current density of 1C, also compare Na0.44MnO2
The capacity of neutral aqueous solution sodium-ion battery is higher by 30 MAhs/g or so, this, which has benefited from alkaline aqueous solution, can substantially reduce electricity
The hydrogen-evolution overpotential in pond, while inhibiting hydrionic insertion in positive electrode.Good performance and cheap cost make it have good
Good Commercial Prospect.
Embodiment 5:
This example describes one kind with tunnel type oxide Na0.5Mn0.9Fe0.1O2For anode, using zinc metal sheet as the alkalinity of cathode
Aqueous solution sodium-ion battery.
(1) anode portion: Na0.5Mn0.9Fe0.1O2Synthesis: sodium acetate, four water second are weighed for 0.5:0.9:0.1 in molar ratio
Sour manganese and ironic citrate are dissolved in dehydrated alcohol, 50~90 DEG C of heating stirrings in heat-collecting magnetic stirring device, while slowly drop
Deionized water to all salt are added to be completely dissolved.Then phenol and formalin are added in mixed solution.Continue heating stirring extremely
The solid that mixed solution becomes gel-like.Gelatinous solid is transferred in 50~100 DEG C of vacuum oven, vacuum drying 8~
15h.Solid after drying is fully ground, and is put into the Muffle furnace under air atmosphere, 700~900 DEG C of 8~15h of calcining.
Na0.5Mn0.9Fe0.1O2The preparation of electrode: Na0.5Mn0.9Fe0.1O2For positive active material, conductive black SP is conduction
The PTFE emulsion of agent, 60wt% is binder, and according to active material: conductive agent: the weight ratio of binder 80: 10: 10 claims
Take active material, conductive agent, binder.First active material and conductive carbon are ground in agate mortar uniformly.Binder is taken again
It is put in small beaker, adds a little isopropanol to be demulsified, ground dusty material is then added, sizes mixing, dry under infrared lamp,
Film forming is finally rolled on twin rollers.Diaphragm is put into 100 DEG C of vacuum drying ovens and keeps 6h or more.It is compressed on stainless (steel) wire.
(2) cathode portion: zinc metal sheet takes the zinc metal sheet of 0.1~1mm of thickness, is polished smooth with sand paper as cathode, and ethyl alcohol rinses
Afterwards, it dries.Suitable shape is cut into scissors.
(3) electrolyte: electrolyte is saturated aqueous sodium carbonate.
Experimental cell is carried out in a U-shaped vial equipped with 10ml electrolyte, and aqueous solution electrolysis is finally assembled into
The sodium-ion battery of liquid.It is tested using constant current charge-discharge mode, charging is 2.0V by voltage, and electric discharge is by voltage
1.15V.Figure 11 is the charging and discharging curve of battery in embodiment 5, and current density is 1C (1C=121 MAhs/g).It can see
Out, under the current density of 1C, battery discharge specific capacity is 76 MAhs/g, also compares Na0.44MnO2Neutral aqueous solution sodium ion
The capacity of battery is higher by 30 MAhs/g or so, this, which has benefited from alkaline aqueous solution, can substantially reduce the hydrogen-evolution overpotential of battery, simultaneously
Inhibit hydrionic insertion in positive electrode.Good performance and cheap cost make it have good Commercial Prospect.
Embodiment 6:
This example describes one kind with tunnel type oxide Na0.5Mn0.9Fe0.1O2For anode, using zinc metal sheet as the alkalinity of cathode
Aqueous solution sodium-ion battery.
(1) anode portion: Na0.5Mn0.9Fe0.1O2Synthesis: sodium acetate, four water second are weighed for 0.5:0.9:0.1 in molar ratio
Sour manganese and ironic citrate are dissolved in dehydrated alcohol, 50~90 DEG C of heating stirrings in heat-collecting magnetic stirring device, while slowly drop
Deionized water to all salt are added to be completely dissolved.Then phenol and formalin are added in mixed solution.Continue heating stirring extremely
The solid that mixed solution becomes gel-like.Gelatinous solid is transferred in 50~100 DEG C of vacuum oven, vacuum drying 8~
15h.Solid after drying is fully ground, and is put into the Muffle furnace under air atmosphere, 700~900 DEG C of 8~15h of calcining.
Na0.5Mn0.9Fe0.1O2The preparation of electrode: Na0.5Mn0.9Fe0.1O2For positive active material, conductive black SP is conduction
The PTFE emulsion of agent, 60wt% is binder, and according to active material: conductive agent: the weight ratio of binder 80: 10: 10 claims
Take active material, conductive agent, binder.First active material and conductive carbon are ground in agate mortar uniformly.Binder is taken again
It is put in small beaker, adds a little isopropanol to be demulsified, ground dusty material is then added, sizes mixing, dry under infrared lamp,
Film forming is finally rolled on twin rollers.Diaphragm is put into 100 DEG C of vacuum drying ovens and keeps 6h or more.It is compressed on stainless (steel) wire.
(2) cathode portion: zinc metal sheet takes the zinc metal sheet of 0.1~1mm of thickness, is polished smooth with sand paper as cathode, and ethyl alcohol rinses
Afterwards, it dries.Suitable shape is cut into scissors.
(3) electrolyte: electrolyte is the 6molL added with zinc oxide-1Sodium hydrate aqueous solution.
Experimental cell is carried out in a U-shaped vial equipped with 10ml electrolyte, and aqueous solution electrolysis is finally assembled into
The sodium-ion battery of liquid.It is tested using constant current charge-discharge mode, charging is 2.0V by voltage, and electric discharge is by voltage
1.15V.Figure 12 is the charging and discharging curve of battery in embodiment 6, and current density is 1C (1C=121 MAhs/g).It can see
Out, under the current density of 1C, battery discharge specific capacity is 76.2 MAhs/g, also compares Na0.44MnO2Neutral aqueous solution sodium from
The capacity of sub- battery is higher by 30 MAhs/g or so, this, which has benefited from alkaline aqueous solution, can substantially reduce the hydrogen-evolution overpotential of battery, together
When inhibit positive electrode in hydrionic insertion.Good performance and cheap cost make it have good Commercial Prospect.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (10)
1. a kind of alkaline aqueous solution sodium-ion battery characterized by comprising
Anode: it is formed by being adhered on collector after positive active material, binder, conductive agent mixing, the positive electrode active material
Matter is NaxMnyNzO2, wherein 0.44≤x≤0.55,0≤y≤1, z=1-y, N Ca, Ti, V, Cr, Mn, Fe ﹑ Co, Ni, Cu,
One or more of Zn, Al ﹑ Zr, Ru metallic element；
Cathode；
Diaphragm；
Electrolyte: solute is the alkaline aqueous solution of sodium salt；
Shell.
2. alkaline aqueous solution sodium-ion battery as described in claim 1, which is characterized in that the positive active material is
NaxMnyNzO2, wherein 0.44≤x≤0.55,0≤z≤0.2, z=1-y.
3. alkaline aqueous solution sodium-ion battery as described in claim 1, which is characterized in that binder is polytetrafluoroethylene (PTFE), gathers
One of vinylidene, polyvinyl alcohol, sodium carboxymethylcellulose, styrene-butadiene latex are a variety of；Conductive agent is graphite, carbon black, iron
One of powder, manganese powder, copper powder, aluminium powder are a variety of；Collector is the paillon or net of titanium, copper, aluminium, stainless steel, nickel.
4. alkaline aqueous solution sodium-ion battery as described in claim 1, which is characterized in that the enclosure material be selected from glass,
The composite material of metal, inorganic matter ceramics, plastics, rubber, resin or metal and plastics, rubber and resin composition；The battery
Form be button, column or Soft Roll.
5. alkaline aqueous solution sodium-ion battery as described in claim 1, which is characterized in that the negative electrode material is by negative electrode active
It is adhered on collector and obtains after substance, binder, conductive agent mixing, the negative electrode active material is that can inhale in stabilized aqueous solution
The electrode material of desorption, deintercalation sodium ion.
6. alkaline aqueous solution sodium-ion battery as described in claim 1, which is characterized in that the negative electrode material is zinc metal sheet or zinc
Powder.
7. alkaline aqueous solution sodium-ion battery as described in claim 1, which is characterized in that the diaphragm is selected from non-woven fabrics, glass
Glass fiber, porous PP/PE diaphragm, PVDF or PTFE film.
8. alkaline aqueous solution sodium-ion battery as described in claim 1, which is characterized in that the electrolyte solute sodium salt is hydrogen
Sodium oxide molybdena, sodium carbonate, sodium bicarbonate, sodium phosphate, disodium-hydrogen, sodium sulfite one or more, the electrolyte solution
Molar concentration be 0.5-10molL-1。
9. alkaline aqueous solution sodium-ion battery as described in claim 1, which is characterized in that be added in the electrolyte solution
Additive.
10. alkaline aqueous solution sodium-ion battery as described in claim 1, which is characterized in that the positive active material
NaxMnyNzO2The preparation method is as follows:
It (1) is that x:y:z weighs sodium acetate, four water manganese acetates and containing the salt of N, mixing is dissolved in dehydrated alcohol by Na, Mn, N molar ratio
In the mixing liquid of water, 50~90 DEG C of heating stirring to salt are completely dissolved, and phenol then is added and formalin continues to heat
Stirring makes mixed solution become gel-like solid；
(2) gained gelatinous solid is dried in vacuo to 8~15h at 50~100 DEG C；
(3) solid after drying is fully ground, 700~1000 DEG C of 8~15h of calcining, obtain Na in air atmospherexMnyNzO2
Positive active material.
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