CN103401030B - A kind of water system can be filled magnesium or zinc ion capacitor batteries - Google Patents

A kind of water system can be filled magnesium or zinc ion capacitor batteries Download PDF

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CN103401030B
CN103401030B CN201310285699.6A CN201310285699A CN103401030B CN 103401030 B CN103401030 B CN 103401030B CN 201310285699 A CN201310285699 A CN 201310285699A CN 103401030 B CN103401030 B CN 103401030B
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magnesium
zinc
ion
water
aqueous solution
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CN201310285699.6A
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CN103401030A (en
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曹殿学
袁聪俐
张莹
韦小培
王贵领
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哈尔滨工程大学
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    • 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 present invention is to provide a kind of water system and can fill magnesium or zinc ion capacitor batteries. Described positive plate comprises plus plate current-collecting body and be coated in the coating that comprises positive active material on plus plate current-collecting body, and described positive active material is three-dimensional tunnel spinel structure λ-MnO2; Described negative plate comprises negative current collector and is coated in the coating of the negative electrode active material on negative current collector, and described negative electrode active material is the carbon based material with the ultracapacitor that the ion of loose structure can adsorption desorption; Described electrolyte is the aqueous solution that contains magnesium ion or the aqueous solution of zinc ion, and in electrolyte, magnesium ion or zinc ion concentration are 0.5mol/L~10mol/L. The present invention uses aqueous electrolyte, has reduced cost, has improved security performance, non-environmental-pollution; Have extended cycle life, energy density is large, is suitable for high current charge-discharge, is a kind of power storage equipment with wide application prospect.

Description

A kind of water system can be filled magnesium or zinc ion capacitor batteries
Technical field
The invention belongs to technical field of electrochemistry, be specifically related to a kind of magnesium/zinc ion capacitor batteries.
Background technology
At present, renewable and clean energy resource is as solar energy, and wind energy etc. become the study hotspot of various countries, but the peak value of these energyThe needs of output and the energy often can not mate, and therefore a kind of efficient, stable, reliable energy conversion and storage device becomeThe problem that we are concerned about most. People have developed the energy storage device of various ways, wherein lithium ion battery since commercialization,With the advantage of its high-energy-density, capture rapidly the market of energy storage device, and at video camera, mobile phone, notebook computer etc.In device, be widely used, but there is potential safety hazard in the flammable organic electrolyte adopting, suppressed in the time of super-charge super-dischargeThe application of lithium ion battery in large-scale energy storage device; Meanwhile, lithium ion battery is also subject to fast charging and discharging and cycle performance number of timesRestriction; Compare with battery with traditional capacitor, ultracapacitor specific power is high, have discharge and recharge fast, have extended cycle life,The features such as serviceability temperature wide ranges, but the energy storage density of ultracapacitor is lower, more than not going up battery. As everyone knows, batteryBe that energy storage is carried out in the deintercalation in electrode material by ion, and the charge storage of ultracapacitor is to occur in electrode/electrolyteOn the electric double layer of interface formation, mainly carry out the mode such as underpotential deposition and electrochemistry adsorption desorption with electrode surface and carry out energy storage.
Summary of the invention
The object of the present invention is to provide one to discharge and recharge that speed is fast, energy storage density is high, have extended cycle life, cost is low, Er QiewuThe water system of environmental pollution can be filled magnesium or zinc ion capacitor batteries.
The object of the present invention is achieved like this: comprise the order assembling according to titanium frame, positive plate, barrier film, negative plate, titanium frameThe power brick becoming, power brick is immersed in electrolyte;
Described positive plate comprises plus plate current-collecting body and is coated in the coating that comprises positive active material on plus plate current-collecting body, just describedUtmost point active material is three-dimensional tunnel spinel structure λ-MnO2
Described negative plate comprises negative current collector and the coating that is coated in the negative electrode active material on negative current collector, and described negative pole is livedProperty material is the carbon based material with the ultracapacitor that the ion of loose structure can adsorption desorption;
Described electrolyte is the aqueous solution that contains magnesium ion or the aqueous solution of zinc ion, and in electrolyte, magnesium ion or zinc ion concentration are0.5mol/L~10mol/L。
The present invention can also comprise:
1, three-dimensional tunnel spinel structure λ-MnO2Adopt with the following method and obtain: according to LiMn2O4With H+Mol ratio beThe ratio of 1:1~1:16 is by LiMn2O4Mix with acid, magnetic agitation is carried out the de-lithium of acidleach, and wherein the de-lithium temperature of acidleach is30 DEG C~100 DEG C, the de-lithium time of acidleach is 3h~48h.
2, described in, comprise in the coating of positive active material and also comprise conductive electrode and binding agent, described conduction is Ketjen black, acetylene veryBlack, carbon black or CNT; Described binding agent is Kynoar, acrylonitrile multiple copolymer, polytetrafluoroethylene (PTFE), butylbenzene rubberGlue or sodium carboxymethylcellulose; Described positive and negative collector adopts charcoal cloth, carbon paper, nickel foam, nickel sheet, titanium sheet or stainless (steel) wire.
The carbon based material 3, with the ultracapacitor that the ion of loose structure can adsorption desorption be active carbon, NACF,Charcoal-aero gel or CNT.
4, magnesium ion the aqueous solution be one or more the aqueous solution in magnesium sulfate, magnesium nitrate, magnesium chloride or magnesium dihydrogen phosphate;The aqueous solution of described zinc ion is one or more the aqueous solution of zinc sulfate, zinc nitrate, zinc chloride or zinc dihydrogen phosphate.
5, in described electrolyte, being added with weight ratio content is 1%~5% additive, and described additive is vinylene carbonate, 1,3-propane sultone, propylene sulfite, the mixture of one or more in ethyl sulfate or glycol sulfite.
For the advantage in conjunction with lithium ion battery and ultracapacitor, the present invention proposes one and there is high-energy-density and Gao BiThe water system of power can be filled magnesium/zinc ion capacitor batteries, by magnesium/zinc ion in electrolyte at positive electrode λ-MnO2Embedding de-, cloudy fromSon carries out energy storage at negative pole carbon based material surface adsorption desorption; Meanwhile, magnesium ion of the present invention and zinc ion belong to divalent ion,Be the twice of water system sodium-ion battery and lithium ion battery intermediate ion electric charge, sodium ion or lithium ion embed λ-MnO2Middle storageThe electric charge of an electronics, described water system can be filled magnesium/zinc ion capacitor batteries, and magnesium ion or zinc ion embed λ-MnO2StorageThe electric charge of depositing is the twice of water system sodium ion or lithium ion battery, and therefore, this water system can be filled magnesium/zinc ion capacitor batteries and be had brightAobvious energy storage advantage, it can be used as large-scale energy-storage system, meets the current extensive solar energy increasing and wind energy to charging and discharging fastThe demand of storage device electric.
The operation principle that water system of the present invention can be filled magnesium/zinc ion capacitor batteries is: when electric discharge, the magnesium/zinc ion in electrolyte embedsλ-MnO28a or 16c room in; Meanwhile, the Anion-adsorption in electrolyte is on the surface of negative pole carbon based material,Discharge electric energy. When charging, magnesium/zinc ion is from λ-MnO2In deviate from, meanwhile, anion is desorption from carbon based material, negative and positiveIon meets in electrolyte. In charge and discharge process, relate to converging and separating of zwitterion in electrolyte. The present invention is comprehensiveCarbon based material in the electric double layer capacitance mechanism of the attached generation of capacitor intermediate ion desorption and magnesium/Zinc ion battery magnesium/zinc ion at electricityDeintercalation mechanism in utmost point material, and electrolyte adopt be the water system salting liquid of high conductivity, therefore claim the present invention be water system can fill magnesium/Zinc ion capacitor batteries.
What water system provided by the invention can fill that magnesium/zinc ion capacitor batteries overcome organic system secondary cell in the past requires the non-water severeCarve the shortcoming of environment, use aqueous electrolyte, reduced cost, improved security performance, non-environmental-pollution; Water system can fill magnesium/Zinc ion capacitor batteries operating voltage range 0~2.2V, has extended cycle life, and energy density is large, is suitable for high current charge-discharge, isA kind of power storage equipment with wide application prospect.
Brief description of the drawings
Fig. 1 is λ-MnO that in the embodiment of the present invention 1 and 2 prepared by different condition2XRD figure. Wherein: A leaching time3h; B leaching time 12h.
Fig. 2 is λ-MnO in the embodiment of the present invention 1 and 22At MgSO4What in solution, single electrode was tested charges and discharge electrograph. Wherein: (a)λ-MnO2The leaching time 3h(b of preparation) λ-MnO2The leaching time 12h of preparation.
Fig. 3 is that in the embodiment of the present invention 3, water system can be filled magnesium ion capacitor batteries AC//λ-MnO2High rate performance figure.
Fig. 4 is that in example 4 of the present invention, water system can be filled zinc ion capacitor batteries AC//λ-MnO2Cycle performance figure.
Detailed description of the invention
Water system provided by the invention can be filled magnesium/zinc ion capacitor batteries, and its structure is mainly by titanium frame, positive pole, barrier film, negative pole and titaniumThe sandwich structure that frame forms and electrolyte composition. Wherein:
What the active material of described positive pole adopted is by LiMn2O4The three-dimensional tunnel spinel structure λ-MnO preparing after acidleach2,LiMn2O4The Li on surface2O and MnO dissolve after the de-lithium of acid solution, LiMn2O4Structure cell has slight contraction, finally obtainsλ-MnO2Product even particle size. LiMn2O4Stir acidleach de-lithium, wherein LiMn at specified requirements lower magnetic force2O4WithH+Mol ratio be 1:1~1:16, the de-lithium temperature of acidleach is 30 DEG C~100 DEG C, the de-lithium time of acidleach is 3h~48h.
What the active material of described negative pole adopted is has the charcoal base material of the ultracapacitor that the ion of loose structure can adsorption desorptionMaterial, for example active carbon, NACF, charcoal-aero gel, CNT.
In described both positive and negative polarity pole piece, add appropriate conductive electrode (as Ketjen black, acetylene black, carbon black, CNT or otherConductive material etc.) and binding agent (as Kynoar, acrylonitrile multiple copolymer, polytetrafluoroethylene (PTFE), butadiene-styrene rubber, carboxylic firstBase sodium cellulosate etc.); The collector of described both positive and negative polarity pole piece adopts charcoal cloth, carbon paper, nickel foam, nickel sheet, titanium sheet, stainless (steel) wireDeng.
Described electrolyte is the aqueous solution that contains magnesium ion or zinc ion. The electrolyte of magnesium ion capacitor batteries is magnesium sulfate, nitric acidThe aqueous solution such as magnesium, magnesium chloride, magnesium dihydrogen phosphate or wherein several mixed aqueous solution; The electrolyte of zinc ion capacitor batteries is sulphurThe aqueous solution such as acid zinc, zinc nitrate, zinc chloride, zinc dihydrogen phosphate or wherein several mixed aqueous solution. For improving capacitor batteriesCycle life and ionic conductivity, can add appropriate additive (1%~5%) in electrolyte, for example, and vinylene carbonate,1,3-propane sultone, propylene sulfite, ethyl sulfate, the mixture of one or more in glycol sulfite.In electrolyte, magnesium ion or zinc ion concentration are 0.5mol/L~10mol/L.
The preparation of described pole piece: electrode pastes is mixed by both positive and negative polarity active material, binding agent, conductive electrode, by electrode pastesApply (thickness 400 μ m~1000 μ m) on collector, and at 100 DEG C vacuum drying 20h, coated pole piece is existed(0~10MPa) compressing tablet under certain pressure, is cut into the pole piece of 1cm × 1cm.
The assembling of described sandwich structure: dress up similar Sanming City according to titanium frame, positive plate, barrier film, negative plate, titanium frame der groupControl the power brick of structure, be immersed in the electrolyte system that contains magnesium ion or zinc ion.
The present invention be described in more detail below with instantiation in order to illustrate better.
Embodiment 1
(1) with the mol ratio of 1:2 by LiMn2O4And H2SO4Abundant magnetic agitation 3h at 50 DEG C, through decant, ultrasonic,Centrifugal, filter, after dry, grinding etc. processes, finally prepare product λ-MnO2, XRD characterizes as shown in A in Fig. 1;
(2) by λ-MnO2, Ketjen black, Kynoar be fully mixed into slurry under magnetic agitation according to 8:1:1 mass ratio,Evenly be coated on collector nickel sheet, after drying in 100 DEG C of vacuum drying chambers, cut and make electrode.
(3) pole piece coating thickness is 400 μ m, and every pole piece area is 1cm × 1cm, and the one side coated weight of electrode is 5mg/cm;
(4), to prepare electrode as working electrode, saturated calomel electrode, platinum electrode are respectively reference electrode and electrode are formed to three electricityPolar body system carries out electrochemical property test, and electrolyte is 1mol/LMgSO4Solution;
(5) charging and discharging curve is as shown in Fig. 2 (a), in-0.8V~1V operation interval, charges and discharge with different current densitiesElectrical testing; In the time that low current density 13.6mA/g discharges and recharges, specific discharge capacity has reached 292.4mAh/g, and coulomb efficiency reaches 95%.
Embodiment 2
(1) with the mol ratio of 1:2 by LiMn2O4And H2SO4Abundant magnetic agitation 12h at 50 DEG C, through decant, ultrasonic,Centrifugal, filter, after dry, grinding etc. processes, finally prepare product λ-MnO2, XRD characterizes as shown in B in Fig. 1;
(2) by λ-MnO2, acetylene black, Kynoar is fully mixed into slurry under magnetic agitation according to 8:1:1 mass ratio,Evenly be coated in collector nickel foam, after drying in 100 DEG C of vacuum drying chambers, cut and make electrode.
(3) pole piece coating thickness is 500 μ m, and every pole piece area is 1cm × 1cm, and the one side coated weight of electrode is 6mg/cm;
(4), to prepare electrode as working electrode, saturated calomel electrode, platinum electrode are respectively reference electrode and electrode are formed to three electricityPolar body system carries out electrochemical property test, and electrolyte is 1mol/LMgSO4Solution;
(5) charging and discharging curve is as shown in Fig. 2 (b), in-0.8V~1V operation interval, charges and discharge with different current densitiesElectrical testing; In the time that low current density 13.6mA/g discharges and recharges, specific discharge capacity has reached 402.8mAh/g, and coulomb efficiency reaches 98%.
Embodiment 3
(1) prepare positive electrode λ-MnO according to the step in example 22, by λ-MnO2, carbon black, Kynoar be according to 8:1:1Mass ratio is fully mixed into slurry under magnetic agitation, is evenly coated on collector carbon paper, in 100 DEG C of vacuum drying chambers, driesAfter dry, cut and make electrode; Pole piece coating thickness is 600 μ m, and every pole piece size is 1cm × 1cm, the one side coated weight of electrodeFor 7mg/cm;
(2) negative pole adopts carbon-based material active carbon, and the preparation method of electrode, conductive electrode, binding agent, collector are identical with positive pole,Pole piece coating thickness is 800 μ m, and every pole piece size is 1cm × 1cm, electrode dual coating quality 14mg/cm;
(3) with λ-MnO2, AC is respectively both positive and negative polarity, is assembled into the capacitor batteries structure of similar sandwich-like with barrier film, titanium frame,Electrolyte adopts 1mol/LMgCl2
(4) carry out charge-discharge test in 0~2.2V operating voltage interval, current density is followed successively by 13.6,27.2,68,136,408,680,1360,2720,4080,6800mA/g, test result is as shown in Figure 3; At low current density 13.6mA/gUnder, first charge-discharge specific capacity reaches 183.3mAh/g, after different current densities discharge and recharge, continues at 13.6mA/g electric currentUnder density, charge and discharge, specific discharge capacity can also keep 174mAh/g.
Embodiment 4
(1) positive electrode adopts λ-MnO prepared by example 22, by λ-MnO2, Ketjen black, Kynoar be according to 8:1:1Mass ratio is fully mixed into slurry under magnetic agitation, is evenly coated on collector charcoal cloth, in 100 DEG C of vacuum drying chambers, driesAfter dry, cut and make electrode;
(2) negative electrode active material adopts carbon based material CNT, and cathode size is according to CNT: Ketjen black: polyvinylidene fluorideThe mass ratio of alkene=8:1:1 is fully mixed into slurry under magnetic agitation, on even coated collector charcoal cloth, and 100 DEG C of vacuum drying;
(3) anode pole piece coating thickness is 800 μ m, and the one side coated weight of electrode is 10mg/cm; Cathode pole piece coating thicknessBe 1000 μ m, the dual coating amount of electrode is 20mg/cm;
(4) with λ-MnO2, AC is respectively both positive and negative polarity, is assembled into the capacitor batteries structure of similar sandwich-like with barrier film, titanium frame,Electrolyte adopts 1mol/LZnSO4
(5) carry out charge-discharge test in 0~2.2V operating voltage interval, circulate after 100 times with the current density of 136mA/g,Capacity is without obvious decay, more than still maintaining 110mAh/g, as shown in Figure 4.
Embodiment 5
(1) prepare positive electrode λ-MnO according to the step in example 22, by λ-MnO2, Ketjen black, acrylonitrile multi-component copolymerThing is fully mixed into slurry under magnetic agitation according to 8:1:1 mass ratio, be evenly coated on collector carbon paper, in 100 DEG C of vacuumAfter drying in drying box, cut and make electrode; Positive plate coating thickness is 600 μ m, and every pole piece size is 1cm × 1cm, electrodeOne side coated weight be 7mg/cm;
(2) negative electrode active material adopts carbon-based material active carbon, the preparation method of electrode, conductive electrode, binding agent, collector andAnodal identical, pole piece coating thickness is 800 μ m, and every pole piece size is 1cm × 1cm, electrode dual coating quality 14mg/cm;
(3) with λ-MnO2, AC is respectively both positive and negative polarity, is assembled into the capacitor batteries structure of similar sandwich-like with barrier film, titanium frame,Electrolyte employing 1,3,6mol/LMg (NO3)2Solution;
(4) carry out charge-discharge test in 0~2.2V operating voltage interval, under the current density of 136mA/g, circulate after 100 times,Specific capacity maintains 120,119 successively, 113mAh/g, and coulomb efficiency all approaches 100%.
Embodiment 6
(1) prepare positive electrode λ-MnO according to example 22, by λ-MnO2, acetylene black, polytetrafluoroethylene (PTFE) is according to 8:1:1 matterAmount, than be fully mixed into slurry under magnetic agitation, is evenly coated on collector charcoal cloth, in 100 DEG C of vacuum drying chambers, driesAfter cut and make electrode;
(2) negative electrode active material adopts carbon based material CNT, and cathode size is according to CNT: acetylene black: polytetrafluoroethyl-neThe mass ratio of alkene=8:1:1 is fully mixed into slurry under magnetic agitation, on even coated collector charcoal cloth, and 100 DEG C of vacuum drying;
(3) positive plate coating thickness is 800 μ m, and every pole piece size is 1cm × 1cm, and the one side coated weight of electrode is 10Mg/cm; Cathode pole piece coating thickness is 1000 μ m, and the dual coating amount of electrode is 20mg/cm;
(4) with λ-MnO2, AC is respectively both positive and negative polarity, is assembled into the capacitor batteries structure of similar sandwich-like with barrier film, titanium frame,Electrolyte adopts 1mol/LZn (NO3)2、Zn(NO3)2+ vinylene carbonate, Zn (NO3)2+ 1,3-propane sultone;
(5) carry out charge-discharge test in 0~2.2V operating voltage interval, under the current density of 136mA/g, circulate after 100 times,Specific capacity maintains 115,120 successively, 118mAh/g, wherein electrolyte Zn (NO3)2Add and insert appropriate additive (carbonic acid AsiaVinyl acetate and 1,3-propane sultone electrolyte) after, cycle performance is significantly improved, after 100 circulations,Capacity is not almost decayed.

Claims (6)

1. water system can be filled magnesium or a zinc ion capacitor batteries, comprises according to titanium frame, positive plate, barrier film, negative plate, titanium frameThe power brick that der group is dressed up, power brick is immersed in electrolyte, it is characterized in that:
Described positive plate comprises plus plate current-collecting body and is coated in the coating that comprises positive active material on plus plate current-collecting body, just describedUtmost point active material is three-dimensional tunnel spinel structure λ-MnO2
Described negative plate comprises negative current collector and the coating that is coated in the negative electrode active material on negative current collector, and described negative pole is livedProperty material is the carbon based material with the ultracapacitor that the ion of loose structure can adsorption desorption;
Described electrolyte is the aqueous solution that contains magnesium ion or the aqueous solution of zinc ion, and in electrolyte, magnesium ion or zinc ion concentration are1mol/L;
Described three-dimensional tunnel spinel structure λ-MnO2Adopt with the following method and obtain: according to LiMn2O4With H+Mol ratioFor the ratio of 1:2 is by LiMn2O4Mix with acid, magnetic agitation is carried out the de-lithium of acidleach, and wherein the de-lithium temperature of acidleach is 50 DEG C, acidSoaking the de-lithium time is 12h.
2. a kind of water system according to claim 1 can be filled magnesium or zinc ion capacitor batteries, it is characterized in that: described in comprise positive poleIn the coating of active material, also comprise conductive agent and binding agent, described conductive agent is carbon black or CNT; Described binding agent is poly-Vinylidene, acrylonitrile multiple copolymer, polytetrafluoroethylene (PTFE), butadiene-styrene rubber or sodium carboxymethylcellulose; Described positive and negative collectorAdopt charcoal cloth, carbon paper, nickel foam, nickel sheet, titanium sheet or stainless (steel) wire.
3. a kind of water system according to claim 1 and 2 can be filled magnesium or zinc ion capacitor batteries, it is characterized in that: described in haveThe ion of loose structure can adsorption desorption the carbon based material of ultracapacitor be NACF, charcoal-aero gel or CNT.
4. a kind of water system according to claim 1 and 2 can be filled magnesium or zinc ion capacitor batteries, it is characterized in that: magnesium ionThe aqueous solution is one or more the aqueous solution in magnesium sulfate, magnesium nitrate, magnesium chloride or magnesium dihydrogen phosphate; The water of described zinc ionSolution is one or more the aqueous solution of zinc sulfate, zinc nitrate, zinc chloride or zinc dihydrogen phosphate.
5. a kind of water system according to claim 3 can be filled magnesium or zinc ion capacitor batteries, it is characterized in that: magnesium ion water-solubleLiquid is one or more the aqueous solution in magnesium sulfate, magnesium nitrate, magnesium chloride or magnesium dihydrogen phosphate; The aqueous solution of described zinc ionFor one or more the aqueous solution of zinc sulfate, zinc nitrate, zinc chloride or zinc dihydrogen phosphate.
6. a kind of water system according to claim 5 can be filled magnesium or zinc ion capacitor batteries, it is characterized in that: in described electrolyteBe added with weight ratio content and be 1%~5% additive, described additive is vinylene carbonate, 1,3-propane sultone, and AsiaSulfuric acid propylene, the mixture of one or more in ethyl sulfate or glycol sulfite.
CN201310285699.6A 2013-07-09 2013-07-09 A kind of water system can be filled magnesium or zinc ion capacitor batteries CN103401030B (en)

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