CN103219551A - Water-system alkali metal ion power storage device - Google Patents

Water-system alkali metal ion power storage device Download PDF

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Publication number
CN103219551A
CN103219551A CN2013101034782A CN201310103478A CN103219551A CN 103219551 A CN103219551 A CN 103219551A CN 2013101034782 A CN2013101034782 A CN 2013101034782A CN 201310103478 A CN201310103478 A CN 201310103478A CN 103219551 A CN103219551 A CN 103219551A
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water
sodium
alkali metal
potassium
active
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方淳
袁超群
戴翔
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Enli energy science and technology limited company
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ENLI ENERGY TECHNOLOGY (NANTONG) Co Ltd
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/36Accumulators not provided for in groups H01M10/05-H01M10/34
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection 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
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to a water-system alkali metal ion power storage device. The water-system alkali metal ion power storage device comprises an anode, a cathode, a membrane and aqueous electrolyte containing alkali metal ion, and is characterized in that the active material of the anode is the multiple transition metal oxide which has the general formula of A1+a(XmYnMn1-m-n)O2+b and contains the alkali metal, wherein A is selected from one or a plurality of Li, Na and K; X and Y are selected from one of Ni, Co, Al, Cr, V, Ti and Fe; m+n is larger than zero and less than one; a is larger than or equal to zero; b is less than one; the crystal structure of the multiple transition metal oxide for the active material of the anode contains a layer structure and reversibly recycles at the capacity of larger than 100 mAh/9. The water-system alkali metal ion power storage device is featured with high capacity, low cost, safety and environmental protection, and applicable to storage apparatuses of all sizes.

Description

A kind of aquo-base metal ion energy storage device
Technical field
The present invention relates to a kind of aquo-base metal ion electrochemical energy storage device.
Background technology
Along with science and technology, economic and social development, the energy and environmental problem more and more receive publicity, energy aspect demand continues to rise suddenly and sharply, the shortage of fossil energy and make focus turn to wind energy, these renewable resources of solar energy to the destruction that environment causes, yet these regenerative resources are subjected to the influence of weather and time period bigger, have tangible instability, characteristics such as discontinuous and uncontrollable, need exploitation and build supporting electrical power storage (energy storage) device to guarantee the continuity and the stability of generating electricity, powering.Therefore, extensive energy storage technology is a key of greatly developing renewable energy utilization such as solar energy, wind energy and intelligent grid.In all energy storage technologies, battery can be realized the effective conversion between chemical energy and the electric energy, is a kind of store energy technology of the best.The rechargeable pond is present most popular a kind of energy storage mode.Compare with other energy storage mode, electrochemical energy storage can adapt to different electrical network function needs, especially has advantage aspect integrated being incorporated into the power networks of wind-powered electricity generation, photoelectricity etc.For the popularization aspect of chargeable battery energy storage technology, there is this two challenge greatly.The firstth, exploitation has high voltage and a high-octane battery system, second be to use cost low, stable, to the complete close friend of environment, long-life battery system, to guarantee that electric energy is incorporated in the electrical network endlessly from renewable and clean energy resource.
At present, be used for the mode of large-scale power grid energy storage, in the case that actual cloth is built, still based on traditional lead-acid battery.But main materials such as the low life-span weak point of lead-acid battery cost, lead and the concentrated sulfuric acid cause severe contamination to environment, need to reclaim.Therefore, press for and find a kind of new technology that can substitute lead-acid battery.
Recent two decades comes, and the development of lithium-ion electric pool technology is increasingly mature, because its energy density is big, the output voltage height makes lithium ion battery also obtain fast development in the application of different field.But, caused manufacturing cost higher and inflammable and explosive potential safety hazard in use arranged thus because lithium ion battery is with an organic solvent as electrolyte.Chinese patent Granted publication CN1328818C discloses a kind of mixed aquo-lithium ion battery.Its operation principle is: to the battery of dressing up, at first must charge.In the charging process, lithium ion is deviate from from positive pole, and by electrolyte, lithium ion is adsorbed on the negative pole that materials such as activated carbon are made.In the discharge process, lithium ion desorption from the negative pole, by electrolyte, lithium ion embeds anodal.Charge and discharge process only relates to lithium ion in two interelectrode transfers.The positive electrode of this mixed aquo-lithium ion battery adopts LiMn 2O 4, LiCoO 2, LiCo 1/3Ni 1/3Mn 1/3O 2, LiMg 0.2Mn 1.8O 4Deng the material of can reversible embedding deviating from lithium ion, negative pole then adopts specific area at 1000m 2Active carbon, mesoporous carbon or carbon nano-tube etc. that/g is above.
In addition, along with the large-scale application of lithium ion battery, the demand of lithium can be increasing, because limited reserves in the earth's crust, causes the price of lithium material can be more and more higher.People begin to pay close attention to alkali metal such as the sodium with more cheap in recent years, and potassium or even alkaline-earth metal magnesium replace lithium and is used for energy storage device.The reserves of sodium in the earth's crust are very abundant, account for 2.74%, are the 6th to enrich element, and widely distributed, the cost of material that contains sodium is lower; And the electrochemical properties similar with lithium, the battery of sodium base becomes the alternative of lithium ion battery gradually.
The sodium sulphur and the Na/NiCl based on the sodium metal of early stage research 2Battery, though have comparatively desirable energy density, the sodium that use molten state is as negative pole, therefore operating temperature needs the heat management system of supporting use great number and special solid ceramic electrolyte between 300~350 ℃.If the solid ceramic electrolyte is in case breakage forms short circuit in addition, the Liquid Sodium of high temperature will directly contact with sulphur, and violent exothermic reaction takes place, and produces 2000 ℃ high temperature, and bigger potential safety hazard is arranged.Based on these backgrounds and reason, the room temperature sodium-ion battery becomes people's research focus again.
Chinese patent publication number CN102027625A discloses a kind of water electrolyte electrochemical secondary energy sources storage device based on sodium ion, the water electrolyte that it comprises anode electrode, can make the sodium cation invertibity take off the cathode electrode of embedding, dividing plate and contain sodium cation, wherein the initial activity cathode electrode material makes alkali metal ion take off the activated cathode electrode material of the alkali metal containing of embedding during being included in the initial charge of this device.This activated cathode electrode material can be the λ-MnO that mixes aluminium 2, NaMnO 2(birnessite structure), Na 2Mn 3O 7, NaFePO 4F, Na 0.44MnO 2This anode electrode comprises porous activated carbon, and electrolyte comprises sodium sulphate.
Chinese patent publication number CN1723578A discloses a kind of sodium-ion battery, comprises positive electrode, negative electrode and electrolyte.Positive electrode comprises a kind of electrochemical active material that can invertibity circulation sodium ion, and negative electrode comprises a kind of carbon that can embed sodium ion.This active material comprises the sodium transition metal phosphate.Transition metal comprises a kind of transition metal that is selected from vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), nickel (Ni), the titanium (Ti) and composition thereof.
Chinese patent publication number CN101241802A discloses a kind of asymmetric water system sodium/kalium ion battery capacitor, is made up of positive pole, negative pole, barrier film and electrolyte.Anodal active material is NaMnO 2, NaCoO 2, NaV 3O 8, NaVPO 4F and Na 2VOPO 4Positive electrode active materials and carbon black, binding agent are mixed, be coated on the nickel screen collector, be pressed into electrode after the oven dry.Active carbon is mixed with conductive agent and binding agent, be uniformly coated on the nickel screen collector, be pressed into electrode after the oven dry.Adopt nonwoven fabrics as barrier film, as electrolyte, be assembled into battery with sodium chloride or sodium sulphate.
But, what more than be studied has spinel structure and birnessite structure manganate or has the phosphate cathode material of nucleocapsid structure, although its theoretical specific capacity is many more than 100mAh/g, but the specific capacity effective capable of circulation in containing the aqueous solution of sodium/potassium ion is low all below 100mAh/g, cause the energy density of device on the low side, become the bottleneck that sodium/potassium ion energy storage technology is promoted, need the novel anode material that exploitation has high power capacity badly, thereby improve the energy density of sodium/potassium energy storage device.
Summary of the invention
In order to develop a kind of high power capacity, low cost, safety, environment-friendly type water system energy storage device, the invention provides a kind of aquo-base metal ion electrochemical energy storage device, the water electrolyte that comprises positive pole, negative pole, barrier film and alkali metal containing ion, it is characterized in that this anodal active material is for having general formula A 1+a(X mY nMn 1-m-n) O 2+bThe polynary transition metal oxide of alkali metal containing, wherein A is selected from one or more among Li, Na and the K; X, Y are selected from a kind of among Ni, Co, Al, Cr, V, Ti and the Fe; 0<m+n<1; 0≤a, b<1, in containing the water electrolyte of sodium or sylvite, the crystal structure of the polynary transition metal oxide of the active material of described positive pole contains layer structure, and described positive pole is with the effective ratio capacity Reversible Cycle greater than 100mAh/g.
In aquo-base metal ion energy storage device of the present invention, the active material of described negative pole can be selected from one or more in active carbon, Graphene, carbon nano-tube, carbon fiber and the mesoporous carbon, these materials all are to carry out non-faraday's electric double layer electronics adsorption process by big surface area, form with positive pole and mix capacitor batteries.Also can be selected from the material of the reversible redox reaction that can in water electrolyte, contain faraday's electronics transfer process.This type of material comprises that alkali metal ion can reversible embedding and take off the oxide of embedding, phosphate material.Be also included within the metal or alloy material that aqueous phase can carry out reversible dissolving and deposition reaction.The reversible redox reaction potential of the negative material that the above-mentioned reversible redox that can contain faraday's electronics transfer process in water electrolyte reacts can not be lower than the hydrogen-evolution overpotential of this water electrolyte, to avoid discharging and recharging owing to the device that generation was caused of this irreversible electrochemical reaction of evolving hydrogen reaction the decline of coulombic efficiency.
In aquo-base metal ion energy storage device of the present invention, the crystal structure of the polynary transition metal oxide of alkali metal of described positive electrode includes layer structure.The polynary transition metal oxide of this alkali metal containing is selected from LiNi 0.33Co 0.33Mn 0.33O 2, LiNi 0.4Co 0.2Mn 0.4O 2, LiNi 0.5Co 0.2Mn 0.3O 2, LiNi 0.5Mn 0.5O 2, NaNi 0.33Co 0.33Mn 0.33O 2, NaNi 0.4Co 0.2Mn 0.4O 2, NaNi 0.5Co 0.2Mn 0.3O 2, NaNi 0.5Mn 0.5O 2, KNi 0.33Co 0.33Mn 0.33O 2, KNi 0.5Co 0.2Mn 0.3O 2, KNi 0.4Co 0.2Mn 0.4O 2, KNi 0.5Mn 0.5O 2In one or more mixture, or the material of the metal of above-mentioned transition metal oxide or nonmetal doping.Doping metals comprises one or more among Li, Mg, Al, Cu, Cr, Mg, Zr, Fe, the Mo.That mixes nonmetally comprises among F, Si, the B one or more.
In aquo-base metal ion energy storage device of the present invention, described water electrolyte is including but not limited to one or more mixed liquors in sodium sulphate, sodium nitrate, sodium halide, sodium carbonate, sodium phosphate, sodium acetate, NaOH, sodium perchlorate, potassium sulfate, potassium nitrate, potassium halide, potash, potassium phosphate, potassium acetate, potassium hydroxide, the potassium hyperchlorate.Concentration of electrolyte is 0.5-10mol.L -1, the pH value is between 3-12.
Low in order to solve existing room temperature water system alkali metal ion cell positive material energy density, the problem that performance is performed poor the invention provides a kind of polynary transition metal oxide positive electrode of alkali metal containing.The polynary transition metal oxide of alkali metal containing of the present invention has general formula A 1+a(X mY nMn 1-m-n) O 2+b, wherein A is selected from one or more among Li, Na and the K; X and Y are selected from a kind of among Ni, Co, Al, Cr, V, Ti and the Fe; 0<m+n<1; 0≤a, b<1.Particularly, the polynary transition metal oxide of described alkali metal containing is selected from LiNi 0.33Co 0.33Mn 0.33O 2, LiNi 0.4Co 0.2Mn 0.4O 2, LiNi 0.5Co 0.2Mn 0.3O 2, LiNi 0.5Mn 0.5O 2, NaNi 0.33Co 0.33Mn 0.33O 2, NaNi 0.4Co 0.2Mn 0.4O 2, NaNi 0.5Co 0.2Mn 0.3O 2, NaNi 0.5Mn 0.5O 2, KNi 0.33Co 0.33Mn 0.33O 2, KNi 0.5Co 0.2Mn 0.3O 2, KNi 0.4Co 0.2Mn 0.4O 2, KNi 0.5Mn 0.5O 2In one or more.The conductive agent (graphite, carbon black, acetylene black etc.) that described positive electrode also need add 1%-10% improves material conductivity, also need add the composite material that the binding agent (polytetrafluoroethylene, Kynoar etc.) of 1%-10% is made evenly, had viscosity simultaneously, again this composite material is fixed on the collector electrode by pressure or conducting resinl.Collector electrode includes stainless steel, nickel, titanium, graphite fiber cloth etc.
The polynary transition metal oxide positive electrode pattern of described alkali metal containing is the class sphere, and the particle that it is characterized in that the class sphere is the second particle that is formed by the primary particle reunion of nanostructure.Wherein the average grain diameter of nano level primary particle is less than 500 nanometers, and the average grain diameter of the spherical second particle of class is in 1 micron to 20 microns scope.
The presoma of the polynary transition metal oxide positive electrode of described alkali metal containing is the synthetic method preparation by co-precipitation.The maximum characteristics of this synthetic method are to be convenient to industrialization.Compare with it, sol-gal process is although hydro thermal method and microwave method etc. are widely used for nano materials in recent years in laboratory scale synthesizing, but owing to have cost of raw material height, complex process, synthesis condition harshness, problems such as synthesis cycle is long are not suitable for extensive industrialization.Especially be not suitable for cost and be regarded as the energy storage material field of popularization and application bottleneck.
The active material of described positive pole is for having general formula A 1+a(X mY nMn 1-m-n) O 2+bThe polynary transition metal oxide of alkali metal containing, wherein said alkali metal A contains lithium (Li), and the described active material that contains the lithium positive pole before described water system electrochemical energy storing device assembling or after the assembling through chemistry or electrochemical alkali metal ion exchange processing.The active material that contains the lithium positive pole can be active material to be positioned in the dilute acid soln soak, thereby lithium ion is broken away from the capable chemical treatment of device assembling advancing.The active material that will contain the lithium positive pole carries out the exchange of electrochemistry alkali metal ion to be handled, be that active material is placed the electrochemical cell that contains sodium or potassium salt soln, in the certain voltage scope, carry out long-time charge and discharge cycles, lithium ion is taken off from the structure of positive electrode, and the structure that makes sodium or potassium ion enter into positive electrode goes, thereby realizes the exchange between sodium or potassium ion and the lithium ion.The exchange of electrochemistry alkali metal ion is handled and can also can be realized by implementing to discharge and recharge activation after the device assembling at device assembling advancing row again.
The polynary transition metal oxide positive electrode of described alkali metal containing all carries out Reversible Cycle with the effective ratio capacity greater than 100mAh/g in different water sodium salts or sylvite electrolyte.
The present invention will realize the application of alkali metal ion positive electrode in water alkali metal ion electrolyte easily, can reduce cost and improve the device security energy.
Description of drawings
Fig. 1 is that positive electrode active materials is LiNi in the embodiment of the invention 1 0.5Co 0.2Mn 0.3O 2The structure chart of-active carbon energy storage device.
Fig. 2 is LiNi in the embodiment of the invention 1 0.5Co 0.2Mn 0.3O 2The charging and discharging curve of-active carbon energy storage device in aqueous sodium persulfate solution.
Fig. 3 is LiNi in the embodiment of the invention 1 0.5Co 0.2Mn 0.3O 2The charging and discharging curve of-active carbon energy storage device in potassium sulfate solution.
Fig. 4 is LiNi in the embodiment of the invention 1 0.5Co 0.2Mn 0.3O 2The charging and discharging curve of-active carbon energy storage device in sodium nitrate aqueous solution.
Fig. 5 is LiNi in the embodiment of the invention 1 0.5Co 0.2Mn 0.3O 2The cycle performance curve of-active carbon energy storage device in sodium nitrate aqueous solution.The the 1st to the 10th circulation discharges and recharges for 0.1C, discharges and recharges for 1C after the 10th circulation.
Fig. 6 is LiNi in the embodiment of the invention 1 0.5Co 0.2Mn 0.3O 2X-ray powder diffraction (XRD) figure.
Fig. 7 is LiNi in the embodiment of the invention 1 0.5Co 0.2Mn 0.3O 2ESEM (SEM) figure.
Fig. 8 is LiNi in the embodiment of the invention 2 0.33Co 0.33Mn 0.33O 2The charging and discharging curve of-active carbon energy storage device in aqueous sodium persulfate solution.
Fig. 9 is LiNi in the embodiment of the invention 3 0.4Co 0.2Mn 0.4O 2The charging and discharging curve of-active carbon energy storage device in potassium sulfate solution.
Embodiment
The present invention will carry out more detailed description by embodiment, but protection scope of the present invention is not limited to these embodiment.
Embodiment 1
Positive electrode active materials adopts business-like LiNi 0.5Co 0.2Mn 0.3O 2Positive electrode is according to LiNi 0.5Co 0.2Mn 0.3O 2: acetylene black: the mass ratio of PTFE binding agent=80:10:10 evenly mixes, and with the mixture roll-in or roll on the stainless (steel) wire, makes the thick electrode slice of 0.2mm then after the oven dry.Negative material adopts business-like active carbon, and according to active carbon: conductive black: the mass ratio of PTFE binding agent=80:10:10 evenly mixes, and with the mixture roll-in or roll on the stainless (steel) wire, makes the thick electrode slice of 1mm then after the oven dry.Then the both positive and negative polarity electrode is cut according to specification, matched group is dressed up the CR2032 button cell, the PP base barrier film that barrier film adopts hydrophilic treated to cross, and electrolyte is respectively 1M Na 2SO 4, 0.5M K 2SO 4, 2M NaNO 3The aqueous solution, battery structure as shown in Figure 1, shown in Fig. 2,3,4, at the voltage range of 0.2V-1.8V, charging and discharging currents is 0.1C to the Reversible Cycle charging and discharging curve, at Na respectively 2SO 4, K 2SO 4, NaNO 3Reversible Cycle specific discharge capacity in the solution is respectively 120.5mAh/g, 148.0mAh/g, 120.9mAh/g.At 2M NaNO 3Discharge cycles curve in the aqueous solution as shown in Figure 5.Fig. 6 is LiNi in the embodiment of the invention 1 0.5Co 0.2Mn 0.3O 2X-ray powder diffraction (XRD) figure.Fig. 7 is LiNi in the embodiment of the invention 1 0.5Co 0.2Mn 0.3O 2ESEM (SEM) figure.Fig. 7 shows that the polynary transition metal oxide positive electrode pattern of this alkali metal containing is the class sphere, such spherical particle is the second particle that is formed by the primary particle reunion of nanostructure, wherein the average grain diameter of nano level primary particle is less than 500 nanometers, and the average grain diameter of the spherical second particle of class is in 1 micron to 20 microns scope.
Embodiment 2
Positive electrode active materials adopts business-like LiNi 0.33Co 0.33Mn 0.33O 2Positive electrode is according to LiNi 0.33Co 0.33Mn 0.33O 2: acetylene black: the mass ratio of PTFE binding agent=80:10:10 evenly mixes, and with the mixture roll-in or roll on the stainless (steel) wire, makes the thick electrode slice of 0.2mm then after the oven dry.Negative material adopts business-like active carbon, and according to active carbon: conductive black: the mass ratio of PTFE binding agent=80:10:10 evenly mixes, and with the mixture roll-in or roll on the stainless (steel) wire, makes the thick electrode slice of 1mm then after the oven dry.Then the both positive and negative polarity electrode is cut according to specification, matched group is dressed up the CR2032 button cell, the PP base barrier film that barrier film adopts hydrophilic treated to cross, and electrolyte is the Na of 1M 2SO 4The aqueous solution, charging and discharging curve is distinguished as shown in Figure 8, and at the voltage range of 0.2V-1.8V, charging and discharging currents is 0.1C, at Na 2SO 4Reversible Cycle specific discharge capacity in the aqueous solution is respectively 122.1mAh/g.
Embodiment 3
Positive electrode active materials adopts business-like LiNi 0.4Co 0.2Mn 0.4O 2Positive electrode is according to LiNi 0.4Co 0.2Mn 0.4O 2: acetylene black: the mass ratio of PTFE binding agent=80:10:10 evenly mixes, and with the mixture roll-in or roll on the stainless (steel) wire, makes the thick electrode slice of 0.2mm then after the oven dry.Negative material adopts business-like active carbon, and according to active carbon: conductive black: the mass ratio of PTFE binding agent=80:10:10 evenly mixes, and with the mixture roll-in or roll on the stainless (steel) wire, makes the thick electrode slice of 1mm then after the oven dry.Then the both positive and negative polarity electrode is cut according to specification, matched group is dressed up the CR2032 button cell, the PP base barrier film that barrier film adopts hydrophilic treated to cross, and electrolyte is 0.5M K 2SO 4The aqueous solution, charging and discharging curve as shown in Figure 9, at the voltage range of 0.2V-1.8V, discharging current is that the Reversible Cycle specific discharge capacity of 0.1C is 118.4mAh/g.
Following table 1 is different polynary transition metal oxide of alkali metal containing and monobasic transition metal oxide (LiMn 2O 4And Na 0.44MnO 2) the comparison of Reversible Cycle specific discharge capacity in containing the aqueous solution that Na, karat gold belong to salt.Wherein the active material of negative material is an active carbon.Charging and discharging currents (multiplying power) is 0.1C, and the charging/discharging voltage interval is 0.2-1.8V.
Table 1
Though described the present invention in the mode of specific embodiment, but be apparent that to those skilled in the art, under the situation of the spirit and scope of the present invention that do not break away from appended claims and limited, can carry out variations and modifications to the present invention, these variations and modification comprise within the scope of the invention equally.

Claims (9)

1. a water system electrochemical energy storing device comprises the electrolytical water electrolyte of positive pole, negative pole, barrier film and alkali metal containing, it is characterized in that the active material of described positive pole is for having general formula A 1+a(X mY nMn 1-m-n) O 2+bThe polynary transition metal oxide of alkali metal containing, wherein A is selected from one or more among Li, Na and the K; X, Y are selected from a kind of among Ni, Co, Al, Cr, V, Ti and the Fe; 0<m+n<1; 0≤a, b<1, the crystal structure of the polynary transition metal oxide of alkali metal containing of the active material of described positive pole contains layer structure, and described positive pole is with the effective ratio capacity Reversible Cycle greater than 100mAh/g, and described electrolyte is the aqueous solution that contains sodium or sylvite.
2. water system electrochemical energy storing device according to claim 1 is characterized in that, the pattern of the polynary transition metal oxide material of described alkali metal containing is that the primary particle with nanostructure is assembled the class sphere that forms the micron order second particle.
3. water system electrochemical energy storing device according to claim 1 is characterized in that, the active material of described positive pole is for having general formula A 1+a(X mY nMn 1-m-n) O 2+bThe polynary transition metal oxide of alkali metal containing, wherein said alkali metal A contains lithium (Li), and the described active material that contains the lithium positive pole before described water system electrochemical energy storing device assembling or after the assembling through chemistry or electrochemical alkali metal ion exchange processing.
4. water system electrochemical energy storing device according to claim 1 is characterized in that, described negative material comprise at least a kind of can be in water electrolyte with sodium ion or/and potassium ion carries out the material of reversible electrochemical reaction.
5. water system electrochemical energy storing device according to claim 1 is characterized in that, described negative material comprises at least a kind ofly can carry out sodium ion or/and potassium ion embeds and takes off the material of embedding in water electrolyte.
6. water system electrochemical energy storing device according to claim 1 is characterized in that, the active material of described negative pole is selected from one or more materials in active carbon, Graphene, carbon nano-tube, carbon fiber and the mesoporous carbon.
7. water system electrochemical energy storing device according to claim 1 is characterized in that, described water electrolyte includes one or more in sodium salt, the sylvite electrolyte.
8. water system electrochemical energy storing device according to claim 1, it is characterized in that described water electrolyte is selected from one or more in sodium sulphate, sodium nitrate, sodium halide, sodium carbonate, sodium phosphate, sodium acetate, NaOH, sodium perchlorate, potassium sulfate, potassium nitrate, potassium halide, potash, potassium phosphate, potassium acetate, potassium hydroxide, the potassium hyperchlorate.
9. water system electrochemical energy storing device according to claim 1 is characterized in that, the polynary transition metal oxide of described alkali metal containing is selected from LiNi 0.33Co 0.33Mn 0.33O 2, LiNi 0.4Co 0.2Mn 0.4O 2, LiNi 0.5Co 0.2Mn 0.3O 2, LiNi 0.5Mn 0.5O 2, NaNi 0.33Co 0.33Mn 0.33O 2, NaNi 0.4Co 0.2Mn 0.4O 2, NaNi 0.5Co 0.2Mn 0.3O 2, NaNi 0.5Mn 0.5O 2, KNi 0.33Co 0.33Mn 0.33O 2, KNi 0.5Co 0.2Mn 0.3O 2, KNi 0.4Co 0.2Mn 0.4O 2, KNi 0.5Mn 0.5O 2In one or more mixture, or the material of the metal of above-mentioned transition metal oxide, nonmetal doping.
CN2013101034782A 2013-03-27 2013-03-27 Water-system alkali metal ion power storage device Pending CN103219551A (en)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103259009A (en) * 2013-04-18 2013-08-21 恩力能源科技(南通)有限公司 Water system alkaline metal ion electrochemical energy-storing device
CN104064824A (en) * 2014-06-10 2014-09-24 恩力能源科技(南通)有限公司 Water system rechargeable battery
WO2014153957A1 (en) * 2013-03-27 2014-10-02 恩力能源科技(南通)有限公司 Water-based alkali metal ion energy storage device
CN104347894A (en) * 2013-08-02 2015-02-11 中国人民解放军63971部队 A sedimentary type aqueous lithium ion battery
CN106057477A (en) * 2016-07-22 2016-10-26 清华大学 Water system rechargeable sodion capacitor battery and preparation method thereof
CN106935909A (en) * 2017-05-08 2017-07-07 山东大学 A kind of flame retardant type kalium ion battery electrolyte and preparation method thereof
CN107004868A (en) * 2014-11-26 2017-08-01 3M创新有限公司 Anode material for sodium ion battery and preparation method thereof
CN107634215A (en) * 2017-08-28 2018-01-26 山东大学 A kind of new kalium ion battery positive electrode K0.27MnO2Preparation method
CN107871903A (en) * 2017-05-15 2018-04-03 中国科学院金属研究所 A kind of electric capacity negative pole/insertion positive-type water system sodium ion capacitor batteries
CN108390026A (en) * 2018-01-22 2018-08-10 李慧 A kind of cage positive electrode and its preparation method and application
CN108630458A (en) * 2017-03-20 2018-10-09 北京大学深圳研究生院 A kind of aqueous electrolyte and its application
CN109103457A (en) * 2018-08-09 2018-12-28 吉林大学 Nano-porous gold/potassium vanadate | | aqueous potassium ion micro cell of nano-porous gold/potassium manganate and its preparation method and application
US20190067696A1 (en) * 2015-12-07 2019-02-28 National Institute Of Advanced Industrial Science And Technology Potassium compound and positive electrode active material for potassium ion secondary batteries containing same
CN109524248A (en) * 2018-12-06 2019-03-26 中国科学院兰州化学物理研究所 A kind of construction method of zinc ion mixed capacitor

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1674347A (en) * 2005-04-21 2005-09-28 复旦大学 Mixed aquo-lithium ion battery
CN101154745A (en) * 2007-09-20 2008-04-02 复旦大学 Hydrographical rechargeable lithium or sodium ion battery
CN101241802A (en) * 2008-03-13 2008-08-13 复旦大学 A non symmetric water natrium/kalium ion battery capacitor
JP2010129509A (en) * 2008-12-01 2010-06-10 Sanyo Electric Co Ltd Nonaqueous electrolyte battery

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102055029A (en) * 2010-12-17 2011-05-11 复旦大学 High-safety aqueous and organic mixed lithium 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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1674347A (en) * 2005-04-21 2005-09-28 复旦大学 Mixed aquo-lithium ion battery
CN101154745A (en) * 2007-09-20 2008-04-02 复旦大学 Hydrographical rechargeable lithium or sodium ion battery
CN101241802A (en) * 2008-03-13 2008-08-13 复旦大学 A non symmetric water natrium/kalium ion battery capacitor
JP2010129509A (en) * 2008-12-01 2010-06-10 Sanyo Electric Co Ltd Nonaqueous electrolyte battery

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014153957A1 (en) * 2013-03-27 2014-10-02 恩力能源科技(南通)有限公司 Water-based alkali metal ion energy storage device
CN103259009A (en) * 2013-04-18 2013-08-21 恩力能源科技(南通)有限公司 Water system alkaline metal ion electrochemical energy-storing device
CN104347894A (en) * 2013-08-02 2015-02-11 中国人民解放军63971部队 A sedimentary type aqueous lithium ion battery
CN104064824A (en) * 2014-06-10 2014-09-24 恩力能源科技(南通)有限公司 Water system rechargeable battery
CN107004868A (en) * 2014-11-26 2017-08-01 3M创新有限公司 Anode material for sodium ion battery and preparation method thereof
US20190067696A1 (en) * 2015-12-07 2019-02-28 National Institute Of Advanced Industrial Science And Technology Potassium compound and positive electrode active material for potassium ion secondary batteries containing same
US10811684B2 (en) * 2015-12-07 2020-10-20 National Institute Of Advanced Industrial Science And Technology Potassium compound and positive electrode active material for potassium ion secondary batteries containing same
CN106057477A (en) * 2016-07-22 2016-10-26 清华大学 Water system rechargeable sodion capacitor battery and preparation method thereof
CN106057477B (en) * 2016-07-22 2019-11-29 清华大学 A kind of water system Na ion chargeable capacitor batteries and preparation method thereof
CN108630458A (en) * 2017-03-20 2018-10-09 北京大学深圳研究生院 A kind of aqueous electrolyte and its application
CN106935909A (en) * 2017-05-08 2017-07-07 山东大学 A kind of flame retardant type kalium ion battery electrolyte and preparation method thereof
CN107871903A (en) * 2017-05-15 2018-04-03 中国科学院金属研究所 A kind of electric capacity negative pole/insertion positive-type water system sodium ion capacitor batteries
CN107634215B (en) * 2017-08-28 2020-11-03 山东大学 Novel potassium ion battery positive electrode material K0.27MnO2Preparation method of (1)
CN107634215A (en) * 2017-08-28 2018-01-26 山东大学 A kind of new kalium ion battery positive electrode K0.27MnO2Preparation method
CN108390026A (en) * 2018-01-22 2018-08-10 李慧 A kind of cage positive electrode and its preparation method and application
CN109103457A (en) * 2018-08-09 2018-12-28 吉林大学 Nano-porous gold/potassium vanadate | | aqueous potassium ion micro cell of nano-porous gold/potassium manganate and its preparation method and application
CN109103457B (en) * 2018-08-09 2021-06-25 吉林大学 Nanoporous gold/potassium vanadate aqueous potassium ion micro-battery and preparation method and application thereof
CN109524248A (en) * 2018-12-06 2019-03-26 中国科学院兰州化学物理研究所 A kind of construction method of zinc ion mixed capacitor

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