CN109687040A - A kind of compressible chargeable Zn-Mg battery and battery-sensor integration device based on the battery - Google Patents

A kind of compressible chargeable Zn-Mg battery and battery-sensor integration device based on the battery Download PDF

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Publication number
CN109687040A
CN109687040A CN201811571696.8A CN201811571696A CN109687040A CN 109687040 A CN109687040 A CN 109687040A CN 201811571696 A CN201811571696 A CN 201811571696A CN 109687040 A CN109687040 A CN 109687040A
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China
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battery
electrolyte
compressible
chargeable
manganese
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CN201811571696.8A
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Chinese (zh)
Inventor
支春义
王子峰
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Chengdu Research Institute City University Of Hong Kong
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Chengdu Research Institute City University Of Hong Kong
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    • 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
    • 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 discloses a kind of compressible chargeable Zn-Mg battery and battery-sensor integration device based on the battery, including anode, cathode and electrolyte, the cathode use the active material based on Zn-ef ficiency, and positive electrode active materials are manganese dioxide;The electrolyte is cross-linked polyacrylamide gel electrolyte, and the synthetic method of the cross-linked polyacrylamide gel electrolyte is as follows: 3~5g monomeric acrylamide, 25~35mg ammonium persulfate initiator and 3~5mg milligrams of N ' N- bismethacrylamides being added in 15~25ml deionized water, are continuously stirred until clarification;Then clear solution is transferred in glass surface ware and is coated again with masking foil, 50~70min is reacted at 50~70 DEG C, obtains hydrogel;Finally hydrogel is placed in the zinc sulfate of 0.8~1.2mol/L and the manganese sulfate electrolyte of 0.05~0.15mol/L and is sufficiently impregnated to get cross-linked polyacrylamide gel electrolyte is arrived.The battery can adapt to larger compression stress while be able to maintain energy-storage property, it can be achieved that the flexibility of energy storage device can elasticity.

Description

A kind of compressible chargeable Zn-Mg battery and battery-sensor collection based on the battery At device
Technical field
The present invention relates to a kind of compressible chargeable Zn-Mg battery and battery-sensor integration device based on the battery.
Background technique
In order to be embodied as flexible wearable power electronic equipment, design and the flexible energy storage device of exploitation become existing rank One of the direction of section novel energy-storing equipment research.However, in electrode/diaphragm/electrode three-layered node of traditional energy storage equipment Design flexibility energy storage equipment is more difficult on the basis of structure.It would therefore be desirable to find new Technology Ways to realize storage The flexibility and elasticity of energy equipment.
Currently, the stretchable energy storage equipment based on stretchable electrode or hydrogel electrolyte, such as stretchable super electricity Container or stretchable battery have been achieved for certain progress.However, the progress of compressible energy storage device is at present also very It is limited, in order to which to corresponding compressible electronic device, if compressible press force snesor is powered, developing one kind can adapt to larger pressure The energy storage equipment that stress under compression is able to maintain energy-storage property simultaneously becomes one of project urgently to be resolved.
Summary of the invention
The purpose of the present invention is to solve above-mentioned technical problems, provide the compressible chargeable Zn-Mg battery of one kind and are based on The battery of the battery-sensor integration device, the battery can adapt to larger compression stress while being able to maintain energy-storage property, can be real The flexibility of existing energy storage device can elasticity.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of compressible chargeable Zn-Mg battery by anode, cathode and containing zwitterion and has ionic conductivity Electrolyte composition, the cathode uses the active material based on Zn-ef ficiency, and positive electrode active materials are manganese dioxide;The electricity Xie Zhiwei cross-linked polyacrylamide gel electrolyte, and the synthetic method of the cross-linked polyacrylamide gel electrolyte is such as Under: by 3~5g monomeric acrylamide, 25~35mg ammonium persulfate initiator and 3~5mg milligrams of N ' N- bismethacrylamides It is added in 15~25ml deionized water, continuously stirs until clarification;Then clear solution is transferred in glass surface ware and is used again Masking foil cladding, 50~70min is reacted at 50~70 DEG C, obtains hydrogel;Hydrogel is finally placed in 0.8~1.2mol/L Zinc sulfate and 0.05~0.15mol/L manganese sulfate electrolyte in sufficiently impregnate to get arrive cross-linked polyacrylamide gel Electrolyte.
Specifically, the negative electrode material is that -1.3~-1.5V is permanent under three-electrode system using graphite paper as collector Potentiometry electro-deposition is prepared for metallic zinc negative electrode material.
Specifically, electrolyte used in the electrodeposition process contain 0.1~0.3mol/L zinc sulfate and 0.4~ The sodium citrate of 0.6mol/L.
Specifically, the positive electrode active materials manganese dioxide is prepared using hydro-thermal method.
More specifically, the method that hydro-thermal method prepares manganese dioxide is as follows: by 0.02~0.04mol manganese sulfate, 1~3ml The potassium permanganate of the sulfuric acid of 0.4~0.6mol/L, 80~100ml deionized water and 15~25ml 0.0.05~0.15mol/L It is sufficiently mixed at room temperature, obtains mixed liquor;Then by mixed liquor be transferred to hydro-thermal apply in and at 100~140 DEG C react 10 ~14h;Hydrothermal product is washed with deionized water to neutrality and is dried in vacuo later, the manganese oxide after being dried;After dry Manganese oxide and conductive agent, binder mixed in N '-methyl pyrrolidone with the ratio of 7:2:1, be then evenly applied to stone On black paper collector.
As a preferred embodiment, the conductive agent is acetylene black;The binder is Kynoar.
The present invention also provides a kind of battery-sensor integration devices, and the battery and pressure sensor is integrated.
Compared with prior art, the invention has the following advantages:
(1) compressibility of the invention in order to improve battery, exploitation have used a kind of polyacrylamide aqueous amine of chemical crosslinking Electrolyte of the gel as Rechargeable zinc ion battery.Compared with common battery diaphragm, polyacrylamide hydrogel has good Good water retention property, at the same it is mutually compatible with the ion in zinc ion electrolyte.Therefore, which, which has, is used as Zinc ion battery The potential quality of gel electrolyte.In order to assign hydrogel preferable mechanical performance, such as elasticity and compressibility, present invention employs N ' N- bismethacrylamide causes polymerized monomer, property with ammonium persulfate to be simultaneously chemically crosslinked monomeric acrylamide Can compared with the existing technology in use with polyacrylamide compared with the preparation method that other additives directly mix, not only have Have not that easy-to-leak liquid, storage time are long, are not susceptible to large area oxidizing and crystallizing, reduces cell sealing and the performances such as require, and preparation side Method and material therefor are easier, and the mechanical performance of electrolyte is enhanced after crosslinking, can achieve and The similar good compressibility of rubber type of material (such as good ionic conduction can be kept under 80% compression strain Rate).At the same time, also obtaining good machinery using the Rechargeable zinc ion battery that the cross-linked polyacrylamide assembles can press Contracting performance and electrochemical energy storage performance.Under a variety of compressive strain effect, battery can express good chemical property, such as fill Specific discharge capacity and cycle performance, even up to or more than the performance measured in aqueous solution.
(2) Rechargeable zinc ion battery of the invention shows good chemical property.Through detecting, in the multiplying power of 1C Under, battery discharge specific capacity reaches 230.5mAh g-1, the specific discharge capacity that is measured under same multiplying power close in aqueous solution 277.5mAh g-1.Also, under 1-5C multiplying power, battery shows good multiplying power conservation rate, is still able to maintain under 5C close 140mAh g-1Specific discharge capacity;Under 4C multiplying power, battery cycle charge-discharge 1000 enclose after can still keep close to 70% just Beginning capacity.
(3) Rechargeable zinc ion battery of the invention shows good compressibility and chemical property.Through detecting, Under 25% compressive strain, under the test of 30 circles, cycle performance of battery holding is stablized undamped;Even if in 0 to 20% past complex strain Under, battery specific capacity is almost undamped, slightly rises instead;It is reduced to 40% again when compressive strain increases to 80% from 40%, electricity Pond specific capacity keeps stablizing, no significant change.Meanwhile discovery is monitored to cell output voltage, even if under external interference, For example hand pressure and quickly hammering, cell output voltage keep stablizing, not be decreased obviously.
(4) when battery of the present invention is used to power to pliable pressure sensor, compared with commercialized alkaline battery, pressure The stable output signal of sensor is similar, even if battery of the present invention is still able to maintain stable output in a compressed state.No Only in this way, its excellent compressibility and flexibility enable battery to integrate with pressure sensor, reflect it as wearable intelligence The potentiality of energy equipment.
Detailed description of the invention
Fig. 1 is that battery structure figure and hydrogel are crosslinked synthetic method.
Fig. 2 is the characterization to hydrogel compressibility and ionic conductivity;Wherein, Fig. 2 (a) is polyacrylamide gel Compression and release photo, Fig. 2 (b) are the electron scanning micrograph that polyacrylamide gel is lyophilized, and 20 microns of scale bar, are schemed 2 (c) be the load-deformation curve under continuous 5 circulations of polyacrylamide gel, and Fig. 2 (d) is the compressive strain from 0 to 77.8% The electrochemical impedance spectrum analysis of lower polyacrylamide gel, Fig. 2 (e) are that lower polyacrylamide gel is strained from 0 to 77.8% Change in resistance curve;Fig. 2 (f) and Fig. 2 (g) is that polyacrylamide hydrogel is used for electric conduction under usual state and compressive state The photo of lightening LED lamp is carried out on road.
Fig. 3 is battery performance characterization;Wherein, Fig. 3 (a) is chargeable Zn-Mg battery in polyacrylamide hydrogel In cyclic voltammetry curve, sweep speed: 5 mv ss;Fig. 3 (b) is the first two circles charging and discharging curve of battery under 1C multiplying power;Fig. 3 (c) For battery under 1-5C multiplying power charging and discharging curve;Fig. 3 (d) is for battery with 4C rate charge-discharge in polyacrylamide hydrogel The performance curve of 1000 circles.
Fig. 4 is that battery compressibility can be with electrochemical stability characterization;Wherein, Fig. 4 (a) is the battery under 25% compressive strain In the cycle performance of 1C multiplying power;Fig. 4 (b) is battery the 1,15th and 30 circle charging and discharging curve under 25% compressive strain;Fig. 4 (c) is Battery strains the charging and discharging curve with 7 circle circulations under 1C multiplying power in 0 and 20%;Fig. 4 (d) recycles pressure in 0 and 20% for battery and answers Specific capacity under becoming;Fig. 4 (e) is charging and discharging curve of the battery under the compressive strain for returning 40% from 40 to 80%;Fig. 4 (f) The specific capacity change curve for being battery in the case where returning 40% compressive strain from 40 to 80%;Fig. 4 (g) is that battery is pressed in finger Under voltage stability;Fig. 4 (h) is the continuous stability for hammering lower cell voltage.
Fig. 5 is integrating with the displaying and battery sensor device that compressible battery is pressure sensor power supply;Wherein, Fig. 5 (a) -5 (c) is the photo that compressible battery is used to power to luminescent screen;Fig. 5 (d) is compressible battery and commercial alkaline Battery is used for the performance comparison powered to sensor;Fig. 5 (e) is that integrating based on Zinc ion battery and pliable pressure sensor is soft Property Intelligent bracelet;Fig. 5 (f) is the sensor signal under different finger pressure dynamics;Fig. 5 (g) is 0.3 to 4 hertz of lower different frequencies Sensor signal.
Specific embodiment
The invention will be further described with embodiment for explanation with reference to the accompanying drawing, and mode of the invention includes but not only limits In following embodiment.
A kind of compressible chargeable Zn-Mg battery is present embodiments provided, simultaneously by anode, cathode and containing zwitterion Electrolyte composition with ionic conductivity, the cathode use the active material based on Zn-ef ficiency, and positive electrode active materials are Manganese dioxide.Referring to Fig. 1 and Fig. 2.
Specifically, the main purpose of the present embodiment is so that polymer dielectric itself and the electricity using the electrolyte The mechanical performance in pond increases, thus the present embodiment exploitation used a kind of polyacrylamide hydrogel of chemical crosslinking as The electrolyte of Rechargeable zinc ion battery, compared with common battery diaphragm, polyacrylamide hydrogel has good water conservation Performance, while mutually compatible with the ion in zinc ion electrolyte, in order to assign hydrogel preferable mechanical performance, such as elasticity and Compressibility, present invention employs N ' N- bismethacrylamides to be chemically crosslinked monomeric acrylamide, and use over cure simultaneously Sour ammonium causes polymerized monomer.Its specific synthetic method is as follows: 3~5g monomeric acrylamide, 25~35mg ammonium persulfate are drawn It sends out agent and 3~5mg milligrams of N ' N- bismethacrylamides is added in 15~25ml deionized water, continuously stir until clarification; Then clear solution is transferred in glass surface ware and is coated again with masking foil, 50~70min is reacted at 50~70 DEG C, is obtained Hydrogel;Finally hydrogel is placed in the zinc sulfate of 0.8~1.2mol/L and the manganese sulfate electrolyte of 0.05~0.15mol/L It sufficiently impregnates to get cross-linked polyacrylamide gel electrolyte is arrived.Chemical crosslinking is benefited from, which obtains Good elasticity has been arrived, specifically, has been obtained except preferable compressibility energy, the chemical property of battery itself can be good It is good to keep even increasing, have benefited from the ionic conductivity for coming into full contact with and improving of electrolyte and electrode material.Outside Boundary's interference, under pressing and hammering, the open-circuit voltage of battery shows good stability.Have benefited from the electrolyte, Ke Yishi Now include the preparation of the integrated devices such as flexible sensor-battery, for application of the future on wearable device have it is wide before Scape.
The present embodiment is prepared for the negative electrode material of Rechargeable zinc ion battery using electro-deposition method.Specifically, described Negative electrode material is that the electro-deposition of -1.3~-1.5V potentiostatic method is prepared for metal under three-electrode system using graphite paper as collector Zinc load material, electrolyte used in the electrodeposition process contain 0.1~0.3mol/L zinc sulfate and 0.4~ The sodium citrate of 0.6mol/L.And the positive electrode active materials manganese dioxide is prepared using hydro-thermal method, specifically includes following step It is rapid: by 0.02~0.04mol manganese sulfate, the sulfuric acid of 1~3ml, 0.4~0.6mol/L, 80~100ml deionized water and 15~ The potassium permanganate of 25ml 0.0.05~0.15mol/L is sufficiently mixed at room temperature, obtains mixed liquor;Then mixed liquor is shifted To hydro-thermal apply in and at 100~140 DEG C react 10~14h;Hydrothermal product is washed with deionized water to neutral and vacuum later It is dry, the manganese oxide after being dried;By the manganese oxide after drying with conductive agent acetylene black, binder Kynoar with 7:2: 1 ratio mixes in N '-methyl pyrrolidone, is then evenly applied on graphite paper collector.By above-mentioned positive and negative anodes Material attachment is in the polyacrylamide hydrogel electrolyte over-assemble previously prepared at battery.
Referring to Fig. 3 and Fig. 4, shown using the Rechargeable zinc ion battery that the polyacrylamide hydrogel electrolyte assembles Good chemical property.Through detecting, under the multiplying power of 1C, battery discharge specific capacity reaches 230.5mAh g-1, close to aqueous solution In the specific discharge capacity 277.5mAh g that measures under same multiplying power-1.In addition to this, under 1-5C multiplying power, battery is shown well Multiplying power conservation rate, be still able to maintain close to 140mAhg under 5C-1Specific discharge capacity.Under 4C multiplying power, battery cycle charge-discharge The initial capacity close to 70% can be still kept after 1000 circles.
It is shown using the Rechargeable zinc ion battery that the polyacrylamide hydrogel electrolyte assembles good compressible Property and chemical property.Through detecting, under 25% compressive strain, under the test of 30 circles, cycle performance of battery holding is stablized undamped. Even if battery specific capacity is almost undamped, slightly rises instead 0 to 20% toward under complex strain.When compressive strain increases from 40% It is added to 80% and is reduced to 40% again, battery specific capacity keeps stablizing, no significant change.Meanwhile cell output voltage is supervised Discovery is surveyed, even if under external interference, for example hand pressure and quickly hammering, cell output voltage keep stablizing, not be decreased obviously.
When being used to power to pliable pressure sensor, compared with commercialized alkaline battery, the output of pressure sensor Signal stabilization is similar, even if the present embodiment battery is still able to maintain stable output in a compressed state.Moreover, excellent Different compressibility and flexibility integrates battery successfully with pressure sensor, and therefore, referring to Fig. 5, the present embodiment is additionally provided A kind of battery-sensor integration device, the battery and pressure sensor is integrated.
Above-described embodiment is only one of the preferred embodiment of the present invention, should not be taken to limit protection model of the invention It encloses, as long as that in body design thought of the invention and mentally makes has no the change of essential meaning or polishing, is solved The technical issues of it is still consistent with the present invention, should all be included within protection scope of the present invention.

Claims (7)

1. a kind of compressible chargeable Zn-Mg battery by anode, cathode and containing zwitterion and has ionic conductivity Electrolyte composition, the cathode use the active material based on Zn-ef ficiency, and positive electrode active materials are manganese dioxide, and feature exists In, the electrolyte be cross-linked polyacrylamide gel electrolyte, and the conjunction of the cross-linked polyacrylamide gel electrolyte It is as follows at method: 3~5g monomeric acrylamide, 25~35mg ammonium persulfate initiator and 3~5mg milligrams of N ' N- dimethyl are double Acrylamide is added in 15~25ml deionized water, continuously stirs until clarification;Then clear solution is transferred to glass surface It is coated again with masking foil in ware, 50~70min is reacted at 50~70 DEG C, obtains hydrogel;Hydrogel is finally placed in 0.8~ It sufficiently impregnates in the zinc sulfate of 1.2mol/L and the manganese sulfate electrolyte of 0.05~0.15mol/L to get crosslinked polypropylene acyl is arrived Aqueous amine gel electrolyte.
2. the compressible chargeable Zn-Mg battery of one kind according to claim 1, which is characterized in that the negative electrode material be with As collector, -1.3~-1.5V potentiostatic method electro-deposition under three-electrode system is prepared for metallic zinc negative electrode material to graphite paper.
3. the compressible chargeable Zn-Mg battery of one kind according to claim 2, which is characterized in that in the electrodeposition process The electrolyte used contains the zinc sulfate of 0.1~0.3mol/L and the sodium citrate of 0.4~0.6mol/L.
4. the compressible chargeable Zn-Mg battery of one kind according to any one of claims 1 to 3, which is characterized in that described Positive electrode active materials manganese dioxide is prepared using hydro-thermal method.
5. the compressible chargeable Zn-Mg battery of one kind according to claim 4, which is characterized in that hydro-thermal method prepares titanium dioxide The method of manganese is as follows: by 0.02~0.04mol manganese sulfate, the sulfuric acid of 1~3ml, 0.4~0.6mol/L, 80~100ml deionization The potassium permanganate of water and 15~25ml 0.0.05~0.15mol/L are sufficiently mixed at room temperature, obtain mixed liquor;Then will Mixed liquor be transferred to hydro-thermal apply in and at 100~140 DEG C react 10~14h;Later by hydrothermal product be washed with deionized water to Neutrality is simultaneously dried in vacuo, the manganese oxide after being dried;By after drying manganese oxide and conductive agent, binder with the ratio of 7:2:1 Example mixes in N '-methyl pyrrolidone, is then evenly applied on graphite paper collector.
6. the compressible chargeable Zn-Mg battery of one kind according to claim 5, which is characterized in that the conductive agent is acetylene It is black;The binder is Kynoar.
7. the battery based on battery described in claim 6-sensor integration device, which is characterized in that by the battery and pressure Sensor integration.
CN201811571696.8A 2018-12-21 2018-12-21 A kind of compressible chargeable Zn-Mg battery and battery-sensor integration device based on the battery Pending CN109687040A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1151087A (en) * 1995-11-21 1997-06-04 杨建生 High efficiency zinc-manganese cell
CN1758468A (en) * 2005-08-26 2006-04-12 南开大学 Manganese bioxide nano-tube/nano-wire polar material and preparation method and use thereof
CN102311605A (en) * 2010-07-08 2012-01-11 中国科学院物理研究所 Gel polymer electrolyte and preparation method thereof
CN102386413A (en) * 2011-11-11 2012-03-21 东莞市迈科科技有限公司 Method for preparing monoclinic lithium vanadium phosphate
CN108520985A (en) * 2018-04-08 2018-09-11 烟台大学 A kind of method and its application improving zinc battery cycle life

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1151087A (en) * 1995-11-21 1997-06-04 杨建生 High efficiency zinc-manganese cell
CN1758468A (en) * 2005-08-26 2006-04-12 南开大学 Manganese bioxide nano-tube/nano-wire polar material and preparation method and use thereof
CN102311605A (en) * 2010-07-08 2012-01-11 中国科学院物理研究所 Gel polymer electrolyte and preparation method thereof
CN102386413A (en) * 2011-11-11 2012-03-21 东莞市迈科科技有限公司 Method for preparing monoclinic lithium vanadium phosphate
CN108520985A (en) * 2018-04-08 2018-09-11 烟台大学 A kind of method and its application improving zinc battery cycle life

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