CN103259009B - A kind of water-system alkali metal ion electrochemical energy storing device - Google Patents
A kind of water-system alkali metal ion electrochemical energy storing device Download PDFInfo
- Publication number
- CN103259009B CN103259009B CN201310135859.9A CN201310135859A CN103259009B CN 103259009 B CN103259009 B CN 103259009B CN 201310135859 A CN201310135859 A CN 201310135859A CN 103259009 B CN103259009 B CN 103259009B
- Authority
- CN
- China
- Prior art keywords
- alkali metal
- mno
- sodium
- anode
- energy storing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to a kind of water-system alkali metal ion electrochemical energy storing devices.A kind of water system electrochemical energy storing device of the invention, the water phase electrolyte including anode, cathode, diaphragm and alkali metal containing ion, which is characterized in that the active material of the anode is with general formula xA2MnO3·(1‑x)AMO2Rich alkali metal manganese based solid solution or compound, wherein A is selected from one of Li, Na and K or a variety of；M is selected from one of transient metal Mn, Ni, Co, Cr, Al, Ru and Fe or a variety of；0≤x≤1, the richness alkali metal manganese based solid solution of the active material of the anode or the crystal structure of compound contain layer structure or spinel structure；The electrolyte is the aqueous solution containing sodium or sylvite；The positive electrode can carry out stable charge and discharge cycles in the electrolyte.Aquo-base electrochemical metal energy storage device of the invention, capacity is high, at low cost, safety and environmental protection, can be used in the energy storage device of various scales.
Description
Technical field
The present invention relates to a kind of water-system alkali metal ion electrochemical energy storing devices.
Background technique
With the development of science and technology, economy and society, energy and environmental problem more and more attention has been paid to hold in terms of the energy by demand
Continuous to rise suddenly and sharply, the shortage of fossil energy and the destruction caused by environment make focus turn to these renewable moneys of wind energy, solar energy
Source, however these renewable energy are affected by weather and period, are had apparent unstable, discontinuous and uncontrollable
The features such as, need to develop and build matched electric energy storage (energy storage) device to guarantee the stability of power generation, power supply.
Therefore, extensive energy storage technology is the key that greatly develop the renewable energy utilizations such as solar energy, wind energy and smart grid.Institute
In some energy storage technologies, the efficient conversion between chemical energy and electric energy is may be implemented in battery, is a kind of optimal energy storage skill
Art.Rechargeable pond is a kind of current most popular energy storage mode.Compared with other energy storage modes, electrochemical energy storage energy
Different power grid function needs are enough adapted to, especially there is advantage at the grid-connected aspect that integrates of wind-powered electricity generation, photoelectricity etc..For chargeable battery
For the popularization practical of energy storage technology, there are this two big challenges.First is the battery system that exploitation has high voltage and high-energy,
Second is that use cost is low, stable, completely friendly to environment, the long-life battery system, with guarantee endlessly electric energy from
It is integrated into power grid in renewable and clean energy resource.
Currently, being used for the mode of large-scale power grid energy storage, it is in the case that practical cloth is built, or with traditional lead-acid battery
It is main.The main materials such as lead-acid battery is at low cost but the service life is short, lead and the concentrated sulfuric acid cause seriously to pollute to environment, need to recycle.
Therefore, there is an urgent need to find a kind of new technology that can substitute lead-acid battery.
In the latest 20 years, the development of lithium ion battery technology is increasingly mature, and since its energy density is big, output voltage is high,
So that lithium ion battery is also grown rapidly in the application of different field.But since lithium ion battery uses organic solvent
As electrolyte, it is higher and have inflammable and explosive security risk in use manufacturing cost has been thereby resulted in.Chinese patent is awarded
Power notification number CN1328818C discloses a kind of mixed aquo-lithium ion battery.Its working principle is that: it is first to the battery dressed up
It must first charge.In charging process, lithium ion is deviate from from anode, and by electrolyte, lithium ion is adsorbed on the materials such as activated carbon
Expect the cathode being made into.In discharge process, lithium ion is desorbed from cathode, passes through electrolyte, lithium ion insertion anode.Charge and discharge
Journey only relates to lithium ion in two interelectrode transfers.The positive electrode of the mixed aquo-lithium ion battery uses LiMn2O4、
LiCoO2、LiCo1/3Ni1/3Mn1/3O2、LiMg0.2Mn1.8O4Etc. the material of insertion abjection lithium ion that can be reversible, cathode is then adopted
With specific surface area in 1000m2Active carbon, mesoporous carbon or carbon nanotube of/g or more etc..
In addition, with the large-scale application of lithium ion battery, the demand of lithium can be increasing, due to limited in the earth's crust
Reserves cause the price of lithium material can be higher and higher.People, which begin to focus on, in recent years uses more cheap alkali metal such as sodium, and potassium is very
Replace lithium for energy storage device to being alkaline-earth metal magnesium.Reserves of the sodium in the earth's crust are very rich, account for about 2.74%, are the 6th
Abundant element, widely distributed, the cost of material containing sodium is lower；And electrochemical properties similar with lithium, the battery of sodium base is gradually
Become the alternative of lithium ion battery.
The sodium sulphur and Na/NiCl2 battery based on sodium metal of early stage research, although having ideal energy density,
But the sodium of molten state is used as cathode, running temperature is between 300~350 DEG C, it is therefore desirable to match great number
Heat management system and special ceramiic solid electrolyte.In addition if ceramiic solid electrolyte is once damaged to form short circuit, high temperature
Liquid potassium and sulphur will directly contact, occur violent exothermic reaction, generate 2000 DEG C of high temperature, have biggish safety hidden
Suffer from.Based on these backgrounds and reason, room temperature sodium-ion battery becomes the research hotspot of people again.
China Patent Publication No. CN102027625A discloses a kind of water phase electrolyte electrochemical two based on sodium ion
Secondary energy storage device comprising anode electrode, partition and contains sodium at the cathode electrode that sodium cation invertibity can be made to be embedded in
Cation water phase electrolyte, wherein initial activity cathode electrode material include the device initial charge during make alkali metal
The activated cathode electrode material of the alkali metal containing of ion deinsertion.The activated cathode electrode material can be the λ-MnO for mixing aluminium2、
NaMnO2(birnessite structure), Na2Mn3O7、NaFePO4F、Na0.44MnO2.The anode electrode includes porous activated carbon, and electric
Solving matter includes sodium sulphate.
China Patent Publication No. CN1723578A discloses a kind of sodium-ion battery, including positive electrode, negative electrode and electrolysis
Matter.Positive electrode includes a kind of electrochemical active material for capableing of invertibity circulation sodium ion, and negative electrode includes that one kind can be embedded in
The carbon of kalium ion and natrium ion.The active material includes potassium transition metal phosphate.Transition metal includes being selected from vanadium (V), manganese (Mn), iron
(Fe), one of cobalt (Co), copper (Cu), nickel (Ni), titanium (Ti) transition metal and its mixture.
China Patent Publication No. CN101241802A discloses a kind of non symmetric water natrium/kalium ion battery capacitor,
It is made of anode, cathode, diaphragm and electrolyte.The active material of anode is NaMnO2、NaCoO2、NaV3O8、NaVPO4F and
Na2VOPO4.Positive electrode active materials are uniformly mixed with carbon black, binder, is coated on nickel screen collector, electricity is pressed into after drying
Pole.Active carbon is mixed with conductive agent and binder, is uniformly coated on nickel screen collector, electrode is pressed into after drying.Using nothing
Woven fabric uses sodium chloride or sodium sulphate as electrolyte, is assembled into battery as diaphragm.
But it is above studied with spinel structure and birnessite structure manganate or with the phosphorus of core-shell structure
Hydrochlorate positive electrode, it is effective in the aqueous solution containing sodium ions to potassium ions although its theoretical specific capacity is mostly in 100mAh/g or more
Recyclable specific capacity becomes the popularization of sodium ions to potassium ions energy storage technology in 100mAh/g hereinafter, cause the energy density of device relatively low
A bottleneck, need exploitation have high capacity novel anode material, to improve sodium/potassium energy storage device energy density.
Summary of the invention
In order to develop a kind of high capacity, low cost, safe and environment-friendly type water system energy storage device, the present invention provides a kind of water
It is alkali metal ion electrochemical energy storing device, the water phase electrolyte including anode, cathode, diaphragm and alkali metal containing ion is special
Sign is that the active material of the anode is with general formula xA2MnO3·(1-x)AMO2Rich alkali metal manganese based solid solution or compound
Object, wherein A is selected from one of Li, Na and K or a variety of；M is selected from one of transient metal Mn, Ni, Co, Cr, Al, Ru and Fe
Or it is a variety of；0≤x≤1, the manganese based solid solution of the richness alkali metal of the active material of the anode or the crystal structure of compound contain
Layer structure or spinel structure, and stable structure, the electrolyte are the aqueous solution containing sodium or sylvite；The positive electrode exists
Stable charge and discharge cycles can be carried out in the electrolyte.
In Water-system alkali metal ion power storage device of the invention, the active material of the anode is with general formula
xA2MnO3·(1-x)AMO2Rich alkali metal manganese-based compound in, in the mixed layer of transition metal element and alkali metal element,
Alkali metal and transition metal element form the ordered arrangement of superlattice structure.The material can be A2MnO3Component and AMO2Component
The two forms the manganese base layed solid-solution of stable rich alkali metal, so as to improve layer structure AMO2Stable structure in the circulating cycle
Property.In addition, the material is also possible to A2MnO3Component and AMO2Two-phase of the component on nanoscale is uniformly mixed compound
Object, wherein AMO2Contain spinel structure.
In Water-system alkali metal ion power storage device of the invention, the active material of the cathode can selected from active carbon,
One of graphene, carbon nanotube, carbon fiber and mesoporous carbon are a variety of, these materials are carried out illegally by big surface area
Electric double layer electron adsorption process is drawn, mixes capacitor batteries with anode composition.Can also selected from can in water phase electrolyte into
The material of Reversible redox reaction of the row containing faraday's electronic transfer process.Such material includes that alkali metal ion can
Oxide, the phosphate material of inverse insertion and deintercalation.Reversible dissolution and deposition reaction can be carried out by being also included in water phase
Metal or alloy material.It is above-mentioned that can to carry out the reversible redox containing faraday's electronic transfer process in water phase electrolyte anti-
The Reversible redox reaction current potential for the negative electrode material answered cannot be below the hydrogen-evolution overpotential of the water phase electrolyte, to avoid due to analysis
Hydrogen reacts the decline of device charge and discharge coulombic efficiency caused by the generation of this irreversible electrochemical reaction.
In Water-system alkali metal ion power storage device of the invention, the richness alkali metal manganese based solid solution of the positive electrode or
The crystal structure of compound contains layer structure or spinel structure.The richness alkali metal manganese based solid solution or compound are selected from
xLi2MnO3·(1-x)LiCrO2、xLi2MnO3·(1-x)LiFeO2、xLi2MnO3·(1-x)LiMn2O4、xLi2MnO3·(1-
x)LiNi0.5Mn0.5O2、xLi2MnO3·(1-x)LiNi2/3Mn1/3O2、xLi2MnO3·(1-x)LiFe0.5Ni0.5O2,
xLi2MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2、xLi2MnO3·(1-x)LiNi0.4Co0.4Mn0.2O2、xLi2MnO3·(1-
x)LiNi0.5Co0.2Mn0.3O2、xLi2MnO3·(1-x)NaCrO2、xLi2MnO3·(1-x)NaFeO2、xLi2MnO3·(1-x)
NaNi0.5Mn0.5O2、xLi2MnO3·(1-x)NaNi0.33Co0.33Mn0.33O2、xLi2MnO3·(1-x)NaNi0.4Co0.4Mn0.2O2、
xLi2MnO3·(1-x)NaNi0.5Co0.2Mn0.3O2、xLi2MnO3·(1-x)NaFe0.5Mn0.5O2、xNa2MnO3·(1-x)
NaFeO2、xNa2MnO3·(1-x)NaFe0.5Mn0.5O2、xLi2MnO3·(1-x)KNi0.33Co0.33Mn0.33O2、xLi2MnO3·
(1-x)KNi0.5Co0.2Mn0.3O2、xLi2MnO3·(1-x)KNi0.4Co0.4Mn0.2O2、xLi2MnO3·(1-x)KNi0.5Mn0.5O2
One of (0≤x≤1) or a variety of or above-mentioned rich alkali metal manganese based solid solution or compound are by metal oxide, nonmetallic oxygen
The material of compound cladding.The metal or nonmetal oxide for wherein being used to coat include Al2O3、TiO2、ZnO、CeO2、MgO、ZrO2
Deng.
In Water-system alkali metal ion power storage device of the invention, the richness alkali metal manganese based solid solution of the positive electrode has
There is general formula xA2MnO3·(1-x)AMO2, wherein A is selected from one of Li, Na and K or a variety of；M be selected from transient metal Mn, Ni,
One of Co, Cr, Al, Ru and Fe or a variety of；0≤x≤1.The richness alkali metal manganese based solid solution material can pass through co-precipitation
The synthesis of the methods of method, sol-gal process, solid phase method, hydro-thermal method obtains.Wherein the maximum feature of solid phase method and coprecipitation is just
In industrialization, it is considered as the energy storage material field of popularization and application bottleneck suitable for cost.
In Water-system alkali metal ion power storage device of the invention, the richness alkali metal manganese based solid solution of the positive electrode has
There is general formula xA2MnO3·(1-x)AMO2, wherein A is selected from one of Li, Na and K or a variety of；M be selected from transient metal Mn, Ni,
One of Co, Cr, Al, Ru and Fe or a variety of；0≤x≤1.The material structure can be characterized with X-ray diffractometer,
XRD spectrum can be attributed to space group and beα-NaFeO2 type the layer structure of type.Wherein, the angle of diffraction spreading out between 20 ° -28 °
Caused by penetrating the superlattices ordered arrangement that peak is alkali metal ion and transition metal ions.The alkali metal element of lattice is not entered into
Remain in particle surface, can be washed off through washing.The ratio of alkali metal and transition metal in rich alkali metal manganese based solid solution material
Alkali metal and transition metal content therein can be surveyed after washing, i.e., provable alkali metal element comes into lattice
Portion.
In Water-system alkali metal ion power storage device of the invention, the water phase electrolyte is including but not limited to sulfuric acid
Sodium, sodium nitrate, sodium halide, sodium carbonate, sodium phosphate, sodium acetate, sodium hydroxide, sodium perchlorate, potassium sulfate, potassium nitrate, potassium halide,
One of potassium carbonate, potassium phosphate, potassium acetate, potassium hydroxide, potassium hyperchlorate or a variety of mixed liquors.Concentration of electrolyte is 0.5-
10mol.L-1, pH value is between 3-12.
Low in order to solve existing room temperature water system alkali metal-ion battery positive electrode energy density, performance is bad
Problem, the present invention provides a kind of rich alkali metal manganese based solid solution or composite anode materials.Rich alkali metal manganese base of the invention
Solid solution or compound have general formula xA2MnO3·(1-x)AMO2, wherein A is selected from one of Li, Na and K or a variety of；M is selected from
One of transient metal Mn, Ni, Co, Cr, Al, Ru and Fe are a variety of；0≤x≤1.Specifically, the richness alkali of the positive electrode
Manganese metal based solid solution or compound are selected from xLi2MnO3·(1-x)LiCrO2、xLi2MnO3·(1-x)LiFeO2、xLi2MnO3·
(1-x)LiMn2O4、xLi2MnO3·(1-x)LiNi0.5Mn0.5O2、xLi2MnO3·(1-x)LiNi2/3Mn1/3O2、xLi2MnO3·
(1-x)LiFe0.5Ni0.5O2,xLi2MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2、xLi2MnO3·(1-x)
LiNi0.4Co0.4Mn0.2O2、xLi2MnO3·(1-x)LiNi0.5Co0.2Mn0.3O2、xLi2MnO3·(1-x)NaCrO2、
xLi2MnO3·(1-x)NaFeO2、xLi2MnO3·(1-x)NaNi0.5Mn0.5O2、xLi2MnO3·(1-x)
NaNi0.33Co0.33Mn0.33O2、xLi2MnO3·(1-x)NaNi0.4Co0.4Mn0.2O2、xLi2MnO3·(1-x)
NaNi0.5Co0.2Mn0.3O2、xLi2MnO3·(1-x)NaFe0.5Mn0.5O2、xNa2MnO3·(1-x)NaFeO2、xNa2MnO3·(1-
x)NaFe0.5Mn0.5O2、xLi2MnO3·(1-x)KNi0.33Co0.33Mn0.33O2、xLi2MnO3·(1-x)KNi0.5Co0.2Mn0.3O2、
xLi2MnO3·(1-x)KNi0.4Co0.4Mn0.2O2、xLi2MnO3·(1-x)KNi0.5Mn0.5O2It is one of (0≤x≤1) or more
Kind.The positive electrode also needs conductive agent (graphite, carbon black, acetylene black etc.) Lai Tigao material conductivity that 5%-10% is added, together
When also need the binder (polytetrafluoroethylene (PTFE), Kynoar etc.) that 5%-10% is added be made uniformly, the sticking mixing material of tool
Material, then the mixing material is fixed on collector by pressure or conducting resinl.Collector includes stainless steel, nickel, titanium, graphite
Plate, carbon paper etc..
The active material of the anode is with general formula xA2MnO3·(1-x)AMO2Rich alkali metal manganese based solid solution or multiple
Object is closed, wherein the alkali metal A contains lithium (Li), and the active material of the anode containing lithium is in the water system electrochemical energy storage
It has passed through the alkali metal ion exchange processing of chemistry or electrochemistry before device assembling or after assembling.The active material of the anode containing lithium can
It is that active material is placed in dilute acid soln to impregnate, to make lithium ion to be chemically treated before device assembles
It is detached from.The active material of the anode containing lithium is subjected to electrochemistry alkali metal ion exchange processing, be active material is placed in containing sodium or
In the electrochemical cell of potassium salt soln, long-time charge and discharge cycles are carried out within the scope of certain voltage, make lithium ion from positive material
Taken off in the structure of material, and enter sodium or potassium ion in the structure of positive electrode, thus realize sodium or potassium ion with
Exchange between lithium ion.Electrochemistry alkali metal ion exchange processing can carry out before device assembles, can also be in device group
By carrying out, charge and discharge is electro-active to be realized again after dress.
The present invention will realize application of the alkali metal ion positive electrode in water phase alkali metal ion electrolyte easily, can be with
It reduces cost and improves device security energy.
Detailed description of the invention
Fig. 1 is that positive electrode is 0.16Li in the embodiment of the present invention 12MnO3·0.84LiNi0.4Co0.4Mn0.2O2, cathode material
Material is the structure chart of the energy storage device of active carbon.
Fig. 2 is that positive electrode is 0.16Li in the embodiment of the present invention 12MnO3·0.84LiNi0.4Co0.4Mn0.2O2, with activity
The mixing capacitor batteries of charcoal cathode composition are in 1M Na2SO4Charging and discharging curve in aqueous solution.
Fig. 3 is that positive electrode is 0.16Li in the embodiment of the present invention 12MnO3·0.84LiNi0.4Co0.4Mn0.2O2, with activity
The mixing capacitor batteries of charcoal cathode composition are in 0.5M K2SO4Charging and discharging curve in aqueous solution.
Fig. 4 is that positive electrode is 0.4Li in the embodiment of the present invention 22MnO3·0.6LiNi2/3Mn1/3O2, with activated carbon negative electrode
The mixing capacitor batteries of composition are in 1M Na2SO4Charging and discharging curve in aqueous solution.
Fig. 5 is that positive electrode is 0.4Li in the embodiment of the present invention 22MnO3·0.6LiNi2/3Mn1/3O2X-ray powder spread out
Penetrate (XRD) figure.
Specific embodiment
The present invention will be further described in more detail by specific embodiment, but protection scope of the present invention is not limited to
These embodiments.
Embodiment 1
Positive electrode active materials use Co deposited synthesis nickel cobalt manganese composite hydroxide presoma, then with Li2CO3Mixing
It is obtained afterwards in high-temperature calcination.It is molten that nickel sulfate, manganese chloride, cobalt chloride are prepared into the metal mixed that nickel cobalt manganese total concentration is 2mo1/L
Liquid, wherein Mn:Ni:Co molar ratio is 1:1:1；5mo1/L sodium hydroxide solution is configured using solid piece alkali；It is configured using ammonium hydroxide
100g/L solution；Cocurrent is passed into reaction kettle above-mentioned three kinds of solution simultaneously, temperature of reaction kettle control at 65 DEG C, metallic solution and
The flow of ammonium hydroxide is constant, the pH value 10-11 of sodium hydroxide solution flow control system；Precipitating preparation is washed using vacuum filtration machine washing
Powder product, 110 DEG C of drying obtain Ni1/3Co1/3Mn1/3(OH)2Presoma.By Ni1/3Co1/3Mn1/3(OH)2And Li2CO3It presses
It weighs according to Li/ (Ni+Mn+Co)=1.16:1 molar ratio proportion, then places weighing material in the ball mill with 150rpm ball milling
10h.It obtains uniformly mixed material to be placed in batch-type furnace, 900 DEG C of heat preservation 10h is warming up to 2 DEG C/min, are then naturally cooled to
Room temperature, and smashed and ground, 0.16Li is made2MnO3·0.84LiNi0.4Co0.4Mn0.2O2Dusty material.Positive electrode according to
0.16Li2MnO3·0.84LiNi0.4Co0.4Mn0.2O2: acetylene black: PTFE binder=80:10:10 mass ratio uniformly mixes,
It by mixture roll-in or is rolled by stainless (steel) wire after drying, the electrode slice of 0.2mm thickness is then made.Negative electrode material is using business
The active carbon of change, according to active carbon: conductive black: PTFE binder=80:10:10 mass ratio will mix after being uniformly mixed and dried
It closes object roll-in or is rolled by stainless (steel) wire, the electrode slice of 1mm thickness is then made.Then positive and negative anodes electrode is cut out according to specification
It cuts, pairing is assembled into CR2032 button cell, the PP base diaphragm that diaphragm uses hydrophilic treated to cross, and electrolyte is the Na of 1M2SO4Or
0.5M K2SO4Aqueous solution, battery structure are as shown in Figure 1.Reversible Cycle charging and discharging curve difference is as shown in Figure 2,3.In 0.2V-
The voltage range of 1.8V, charging and discharging currents 0.1C, in Na2SO4And K2SO4The specific capacity of the electric discharge of Reversible Cycle in aqueous solution
It is 123.5mAh/g, 133.5mAh/g respectively.
Embodiment 2
Positive electrode active materials are synthesized using sol-gal process, are 3 according to the stoichiometric ratio of manganese acetate and nickel acetate:
2 weigh manganese acetate respectively, nickel acetate is dissolved in appropriate amount of deionized water, and mixture is placed in 80 DEG C of waters bath with thermostatic control and is stirred, so
The mixed solution of lithium acetate and citric acid is slowly added dropwise afterwards, the molar ratio of lithium acetate and manganese acetate, nickel acetate is 1.47:0.6:
0.4, citric acid and manganese acetate, nickel acetate molar ratio be 1:1:1.Adjusting pH with ammonium hydroxide after dripping off is 7.0-8.0.80 DEG C of heat preservation
Until solution formed gel state, after being dried in 450 DEG C of air atmospheres pre-burning 10h, grind tabletting after again in air atmosphere
In calcine 10h at 900 DEG C, be rapidly cooled to room temperature, obtain 0.4Li2MnO3·0.6LiNi2/3Mn1/3O2Dusty material.Positive material
Material is according to 0.4Li2MnO3·0.6LiNi2/3Mn1/3O2: acetylene black: PTFE binder=80:10:10 mass ratio uniformly mixes,
It by mixture roll-in or is rolled by stainless (steel) wire after drying, the electrode slice of 0.2mm thickness is then made.Negative electrode material is using business
The active carbon of change, according to active carbon: conductive black: PTFE binder=80:10:10 mass ratio will mix after being uniformly mixed and dried
It closes object roll-in or is rolled by stainless (steel) wire, the electrode slice of 1mm thickness is then made.Then positive and negative anodes electrode is cut out according to specification
It cuts, pairing is assembled into CR2032 button cell, the PP base diaphragm that diaphragm uses hydrophilic treated to cross, and electrolyte is the Na of 1M2SO4Water
Solution, charging and discharging curve are as shown in Figure 4.In the voltage range of 0.2V-1.8V, charging and discharging currents 0.1C, in Na2SO4Aqueous solution
The specific capacity of the electric discharge of middle Reversible Cycle is 90.7mAh/g.Fig. 5 is 0.4Li2MnO3·0.6LiNi2/3Mn1/3O2X-ray powder
Last diffraction (XRD) figure.
Table 1 below is different rich alkali metal manganese-based compound and transition metal oxide (LiMn2O4With
Na0.44MnO2) Reversible Cycle specific discharge capacity in the aqueous solution containing Na, karat gold category salt comparison.The wherein work of negative electrode material
Property material be active carbon.Charging and discharging currents (multiplying power) are 0.1C, and charging/discharging voltage section is 0.2-1.8V.
Table 1
It is apparent to those skilled in the art although describing the present invention by way of examples
It is that, in the case where not departing from the spirit and scope of the present invention defined by the appended claims, can be carried out to the present invention
Variations and modifications, these change and modification are also included in the scope of the present invention.
Claims (9)
1. a kind of water system electrochemical energy storing device, the water phase electrolyte including anode, cathode, diaphragm and alkali metal containing ion,
It is characterized in that, the active material of the anode is with general formula xA2MnO3·(1-x)AMO2Rich alkali metal manganese based solid solution or multiple
Object is closed, the specific chemical formula of the active material of the anode is 0.16Li2MnO3·0.84LiNi0.4Co0.4Mn0.2O2Or
0.4Li2MnO3·0.6LiNi2/3Mn1/3O2；The manganese based solid solution of the richness alkali metal of the active material of the anode or compound
Crystal structure contains layer structure or spinel structure；The electrolyte is the aqueous solution containing sodium or sylvite；The positive electrode
Stable charge and discharge cycles can be carried out in the electrolyte.
2. water system electrochemical energy storing device according to claim 1, which is characterized in that the active material of the anode is tool
There is general formula xA2MnO3·(1-x)AMO2Rich alkali metal manganese based solid solution, crystal structure contains layer structure.
3. water system electrochemical energy storing device according to claim 1, which is characterized in that the active material of the anode is tool
There is general formula xA2MnO3·(1-x)AMO2Rich alkali metal manganese-based compound, crystal structure contains spinel structure.
4. water system electrochemical energy storing device according to claim 1, which is characterized in that the active material of the anode is tool
There is general formula xA2MnO3·(1-x)AMO2Rich alkali metal manganese based solid solution or compound, wherein the alkali metal A contains lithium, and
And the active material of the anode containing lithium have passed through chemistry or electricity before water system electrochemical energy storing device assembling or after assembling
The alkali metal ion exchange processing of chemistry.
5. water system electrochemical energy storing device according to claim 1, which is characterized in that the negative electrode material includes at least one
Kind can carry out the material that reversible electrochemical react with sodium ion or/and potassium ion in water phase electrolyte.
6. water system electrochemical energy storing device according to claim 1, which is characterized in that the negative electrode material includes at least one
Kind can carry out the material of sodium ion or/and potassium ion insertion and deintercalation in water phase electrolyte.
7. water system electrochemical energy storing device according to claim 1, which is characterized in that the active material of the cathode is selected from
One of active carbon, graphene, carbon nanotube, carbon fiber and mesoporous carbon or multiple material.
8. water system electrochemical energy storing device according to claim 1, which is characterized in that the water phase electrolyte includes sodium
One of salt, sylvite electrolyte are a variety of.
9. water system electrochemical energy storing device according to claim 1, which is characterized in that the water phase electrolyte is selected from sulfuric acid
Sodium, sodium nitrate, sodium halide, sodium carbonate, sodium phosphate, sodium acetate, sodium hydroxide, sodium perchlorate, potassium sulfate, potassium nitrate, potassium halide,
One of potassium carbonate, potassium phosphate, potassium acetate, potassium hydroxide, potassium hyperchlorate are a variety of.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310135859.9A CN103259009B (en) | 2013-04-18 | 2013-04-18 | A kind of water-system alkali metal ion electrochemical energy storing device |
| PCT/CN2014/070718 WO2014169717A1 (en) | 2013-04-18 | 2014-01-16 | Electrochemical energy storage device of aqueous alkali metal ions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310135859.9A CN103259009B (en) | 2013-04-18 | 2013-04-18 | A kind of water-system alkali metal ion electrochemical energy storing device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103259009A CN103259009A (en) | 2013-08-21 |
| CN103259009B true CN103259009B (en) | 2019-06-14 |
Family
ID=48962808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310135859.9A Active CN103259009B (en) | 2013-04-18 | 2013-04-18 | A kind of water-system alkali metal ion electrochemical energy storing device |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN103259009B (en) |
| WO (1) | WO2014169717A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103259009B (en) * | 2013-04-18 | 2019-06-14 | 恩力能源科技有限公司 | A kind of water-system alkali metal ion electrochemical energy storing device |
| CN103531778A (en) * | 2013-10-28 | 2014-01-22 | 北京理工大学 | Solid solution sodium-ion battery positive material and preparation method therefor |
| CN103854877A (en) * | 2013-12-23 | 2014-06-11 | 燕山大学 | Self-supporting grapheme-manganese oxide combined electrode material and manufacturing method thereof |
| CN105226264B (en) * | 2014-06-16 | 2018-12-14 | 北京理工大学 | A kind of sodium-ion battery richness sodium positive electrode and preparation method thereof and sodium-ion battery |
| CN106602054B (en) * | 2016-12-26 | 2019-08-16 | 东北大学 | Kalium ion battery positive electrode and preparation method thereof, application |
| CN106800312B (en) * | 2017-03-08 | 2019-11-19 | 济南大学 | A kind of preparation method for sodium-ion battery cathode material sodium manganite |
| CN107871861A (en) * | 2017-05-15 | 2018-04-03 | 中国科学院金属研究所 | A water system sodium ion electrochemical energy storage device |
| CN107403915B (en) * | 2017-07-13 | 2020-01-14 | 南京大学 | Manganese-based positive electrode material of sodium ion battery |
| CN109546115A (en) * | 2018-11-19 | 2019-03-29 | 安徽安凯汽车股份有限公司 | A kind of NCA ternary battery of nickelic rich lithium manganese base solid solution positive electrode |
| CN115632117A (en) * | 2022-10-25 | 2023-01-20 | 湖北亿纬动力有限公司 | Manganese-based solid solution cathode material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101241802A (en) * | 2008-03-13 | 2008-08-13 | 复旦大学 | An Asymmetric Aqueous Sodium/Potassium Ion Battery Capacitor |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3539518B2 (en) * | 1995-08-11 | 2004-07-07 | 日立マクセル株式会社 | Lithium secondary battery |
| US10665892B2 (en) * | 2007-01-10 | 2020-05-26 | Eocell Limited | Lithium batteries with nano-composite positive electrode material |
| US20090253025A1 (en) * | 2008-04-07 | 2009-10-08 | Carnegie Mellon University | Sodium ion based aqueous electrolyte electrochemical secondary energy storage device |
| JP5625390B2 (en) * | 2009-03-13 | 2014-11-19 | 住友化学株式会社 | Composite metal oxide, electrode and sodium secondary battery |
| CN102263280A (en) * | 2011-06-28 | 2011-11-30 | 中国科学院物理研究所 | A liquid flow water system rechargeable alkali metal ion battery |
| CN103219551A (en) * | 2013-03-27 | 2013-07-24 | 恩力能源科技（南通）有限公司 | Water-system alkali metal ion power storage device |
| CN103259009B (en) * | 2013-04-18 | 2019-06-14 | 恩力能源科技有限公司 | A kind of water-system alkali metal ion electrochemical energy storing device |
-
2013
- 2013-04-18 CN CN201310135859.9A patent/CN103259009B/en active Active
-
2014
- 2014-01-16 WO PCT/CN2014/070718 patent/WO2014169717A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101241802A (en) * | 2008-03-13 | 2008-08-13 | 复旦大学 | An Asymmetric Aqueous Sodium/Potassium Ion Battery Capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103259009A (en) | 2013-08-21 |
| WO2014169717A1 (en) | 2014-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103259009B (en) | A kind of water-system alkali metal ion electrochemical energy storing device | |
| Liu et al. | Rechargeable aqueous lithium-ion battery of TiO2/LiMn2O4 with a high voltage | |
| CN103441260B (en) | A kind of aqueous alkaline electrochemical energy storing device | |
| CN105958131B (en) | A rechargeable aqueous zinc-ion battery with long cycle life and high energy density | |
| CN103441259B (en) | A kind of high magnification aquo-base metal electrochemical cells positive electrode and preparation method thereof | |
| CN102394297B (en) | Spherical compound lithium-rich multielement cathode material with core shell structure and preparation method thereof | |
| CN103219551A (en) | Water-system alkali metal ion power storage device | |
| CN110277540A (en) | A kind of cathode material of core-shell structure sodium ion battery and its preparation method and application | |
| CN102244236A (en) | Method for preparing lithium-enriched cathodic material of lithium ion battery | |
| WO2023082505A1 (en) | Oxide composite positive electrode material coated with borate in situ, preparation method, and use | |
| CN111162250A (en) | High sodium content P2 phase layered oxide material with valence of pure cation, preparation method and use | |
| CN113078299B (en) | Sodium lithium iron manganese-based layered oxide material, preparation method and application | |
| CN108987711A (en) | A kind of spherical shape sodium-ion battery anode quaternary material and preparation method thereof | |
| CN105810935A (en) | A kind of preparation method of anode material of sodium ion battery | |
| CN106299295B (en) | A kind of porous micro-nano structure lithium-ion battery lithium-rich cathode material with shuttle-shaped morphology and preparation method thereof | |
| CN103078099A (en) | Anode material for lithium ion cell and preparation method thereof | |
| CN103531778A (en) | Solid solution sodium-ion battery positive material and preparation method therefor | |
| CN111600041A (en) | An electrolyte for improving the working voltage of an aqueous zinc-manganese battery and its application | |
| CN102931394B (en) | Lithium nickel manganese oxide material and preparation method thereof, lithium ion battery containing this material | |
| CN113422048A (en) | Preparation method and application of novel water-based zinc ion battery positive electrode material | |
| CN110112473A (en) | A kind of high salt concentration aqueous solution potassium-sodium hybrid ionic battery and application | |
| CN104064824A (en) | Water system rechargeable battery | |
| CN103715422B (en) | Electrolysis prepares the method for the nickelic system positive electrode of lithium ion battery | |
| CN110504443B (en) | Sodium-magnesium-manganese-based layered oxide material with anion valence change, preparation method and application | |
| CN105810932A (en) | Layered cathode material for sodium-ion battery and preparation method of the layered cathode material for the sodium-ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Fang Chun Inventor after: Yuan Chaoqun Inventor after: Dai Xiang Inventor after: Huang Yunhui Inventor after: Zhang Wuxing Inventor after: Jiang Yan Inventor before: Fang Chun Inventor before: Yuan Chaoqun Inventor before: Dai Xiang |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: FANG CHUN YUAN CHAOQUN DAI XIANG TO: FANG CHUN YUAN CHAOQUN DAI XIANG HUANG YUNHUI ZHANG WUXING JIANG YAN |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20171226 Address after: 065000 Hebei Langfang city Guan County Xinchang West Street original party school complex office building Applicant after: ENPOWER ENERGY TECHNOLOGY CO.,LTD. Address before: 226002, No. 8, No. 8, Wen Jun community, happy street, Gangzha District, Jiangsu, Nantong Applicant before: Enli energy technology (Nantong) Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211104 Address after: 100163 101-6, floor 1, building 5, yard 2, Jinsheng street, Daxing District, Beijing Patentee after: Beijing enli Power Technology Co.,Ltd. Patentee after: ENPOWER ENERGY TECHNOLOGY CO.,LTD. Address before: 065000 former party school comprehensive office building, Xinchang West Street, Gu'an County, Langfang City, Hebei Province Patentee before: ENPOWER ENERGY TECHNOLOGY CO.,LTD. |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 100163 101-6, floor 1, building 5, yard 2, Jinsheng street, Daxing District, Beijing Patentee after: Beijing Enli Power Technology Co.,Ltd. Patentee after: ENPOWER ENERGY TECHNOLOGY CO.,LTD. Address before: 100163 101-6, floor 1, building 5, yard 2, Jinsheng street, Daxing District, Beijing Patentee before: Beijing enli Power Technology Co.,Ltd. Patentee before: ENPOWER ENERGY TECHNOLOGY CO.,LTD. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230901 Address after: 100163 101-6, floor 1, building 5, yard 2, Jinsheng street, Daxing District, Beijing Patentee after: Beijing Enli Power Technology Co.,Ltd. Address before: 100163 101-6, floor 1, building 5, yard 2, Jinsheng street, Daxing District, Beijing Patentee before: Beijing Enli Power Technology Co.,Ltd. Patentee before: ENPOWER ENERGY TECHNOLOGY CO.,LTD. |