CN102709624A - Immiscible water/polymer two-phase electrolyte and battery - Google Patents
Immiscible water/polymer two-phase electrolyte and battery Download PDFInfo
- Publication number
- CN102709624A CN102709624A CN2012101647467A CN201210164746A CN102709624A CN 102709624 A CN102709624 A CN 102709624A CN 2012101647467 A CN2012101647467 A CN 2012101647467A CN 201210164746 A CN201210164746 A CN 201210164746A CN 102709624 A CN102709624 A CN 102709624A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- battery
- lithium
- hydrophobic organic
- organic polymer
- 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.)
- Pending
Links
Images
Classifications
-
- 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
Abstract
The invention relates to an immiscible water/polymer two-phase electrolyte and a battery and belongs to the technical field of a chemical power supply. The electrolyte consists of aqueous solution electrolyte and hydrophobic organic polymer electrolyte; the aqueous solution electrolyte is aqueous solution of sulfuric acid, perchloric acid, potassium sulfate, sodium sulfate, potassium hydroxide, sodium hydroxide or copper sulfate; the hydrophobic organic polymer electrolyte consists of a hydrophobic polymer, lithium salt and a hydrophobic organic solvent and has the conductivity of over 10<-4>S/cm; the aqueous solution electrolyte and the hydrophobic organic polymer electrolyte are immiscible and are well contacted and a stable and clear interface is formed; the interface is a flexible, waterproof and oxygen-proof functional region and can replace a rigid solid electrolyte membrane to implement the effect of maintaining the stability of a lithium negative electrode of the battery and the free motion of ions. The immiscible water/polymer two-phase electrolyte can be used for preparing the battery with the lithium negative electrode and is beneficial to the continuous work of the battery. The battery using the electrolyte can be a lithium-air or lithium-metal battery.
Description
Technical field
The present invention relates to a kind of immiscible " water/polymer " two-phase electrolyte and battery; Specifically, relate to a kind of immiscible two-phase electrolyte that forms by aqueous electrolyte and hydrophobic organic polymer electrolyte, and contain the electrolytical battery of said two-phase; Said battery can be lithium-air battery and lithium-metal battery; Wherein, said lithium-metal battery can be lithium-copper battery and lithium-nickel-based battery, belongs to technical field of chemical power.
Background technology
Lithium ion battery is compared with other batteries has many advantages, therefore becomes the research focus at present.Yet the specific energy of lithium ion battery (chemical power source of the organic electrolysis plastidome) positive electrode active materials that adopts is lower, has only 150～220mAhg
-1, and the negative active core-shell material specific energy is very high, for example, the specific energy of silica-based lithium alloy can reach 4400mAhg
-1So,, the specific energy of lithium ion battery mainly receives its positive electrode active materials specific energy quantitative limitation.
The appearance of lithium-air battery is expected to break through lithium ion battery because the specific energy performance deficiency that its positive electrode active materials specific energy restriction causes.Lithium-air battery is a kind of fuel cell, and its negative active core-shell material is the high lithium metal of specific energy, and the specific energy of lithium metal can reach 3860mAhg
-1, anodal is active material with the air or oxygen, the capacity of air positive pole is unrestricted, so the theoretical specific energy of lithium-air battery can be up to 11140Wh/kg.Except air electrode, the specific energy of the metal electrode system in the Water-Electrolyte is also very high, near 300mAhg
-1, almost be 1.5～2 times of anode material for lithium-ion batteries specific energy, so it also is significant developing direction that the metal electrode system of high-energy-density in lithium and the Water-Electrolyte is formed lithium-metal battery.
Because lithium metal is high activity metal, can only in organic electrolyte, work, and can not in water electrolysis liquid, work.But in organic electrolyte, air electrode oxygen in discharge process is reduced and is combined into lithium peroxide (Li with lithium ion in the electrolyte
2O
2) and lithia (Li
2O) deposition, the micropore of obstruction air electrode catalyst causes catalyst to lose catalytic performance.In addition, the metal electrode system in the Water-Electrolyte also can't be worked in organic bath.So,, two-phase electrolyte lithium-air battery and two-phase electrolyte lithium-metal battery have been proposed in order to take into account the operational environment requirement of lithium anode and air electrode, Water-Electrolyte metal electrode system.One of research focus that uses the electrolytical lithium-air battery of two-phase and lithium-metal battery at present is the encapsulation technology of battery structure design, barrier film technology of preparing, function electrolyte preparation technique and battery.The purpose of these researchs is to obtain stable two-phase electrolyte lithium-air battery and lithium-metal battery, wherein, high conductivity, high chemical stability, simultaneously can blocking oxygen, the barrier film or the solid electrolyte that intercept water be key wherein.People such as Yamamoto are primarily aimed at solid electrolyte membrane and conduct a research; The lithium-air battery structure of author designed is: the negative pole at lithium metal uses organic PEO (polyethylene glycol oxide) polyelectrolyte, and anodal air electrode uses aqueous electrolyte, uses between the said two-phase electrolyte and can only separate through the titanium phosphate lithium solid electrolyte of lithium ion; Entire cell can keep continuous discharge (T.Zhang; N.Imanishi, S.Hasegawa, A.Hirano; J.Xie; Y.Takeda, O.Yamamoto, N.Sammes.Li/Polymer Electrolyte/Water Stable Lithium-Conducting Glass Ceramics Composite for Lithium-Air Secondary Batteries with an Aqueous Electrolyte [J] .Journal of the Electrochemical Society; 2008,155 (12): A965-969.).People such as Kumar have compared glass ceramics class Li
1+xAl
xGe
2-x(PO
4)
3(x=0.5) solid electrolyte membrane and PEO and Li
2The performance of the solid electrolyte membrane that O and/or BN (boron nitride) are compound, research shows PEO and Li
2The solid electrolyte membrane that O is compound can reduce interface impedance, improves conductivity, effectively protects negative pole, and the discharge specific energy of related lithium-air battery is expected to surpass 1000Whkg
-1(J.Kumar; B.Kumar.Development of membranes and a study of their interfaces for rechargeable lithium-air battery [J] .Journal of Power Sources; 2009,194 (2): 1113-1119.).Present LISICON (lithium ion conducting pottery) film; Solved the problem that lithium and oxygen directly contact in the lithium-air battery; Guaranteed the stability of negative active core-shell material lithium metal; Also for negative pole provides suitable operational environment, this method is applied for a patent (Ionically conductive composites for protection of active metal anodes, United States Patent 7282302) by Korea S Polyplus Co., Ltd in 2007.People such as Imanishi are assembled in ceramic electrolyte film (LTAP) in the lithium-air battery, and structure is the Li| polymer dielectric | LTAP|1 M LiCl|Pt, however the stability of the lithium-air battery of this structure is better; But internal resistance big (T.Zhang, N.Imanishi, S.Hasegawa; A.Hirano, J.Xie, Y.Takeda; O.Yamamoto; N.Sammes.Water-Stable Lithium Anode with the Three-Layer Construction for Aqueous Lithium-Air Secondary Batteries [J] .Electrochemical and Solid-State Letters, 2009,12 (7): A132-135.).
Above-mentioned present Research also shows; Using these two kinds in aqueous electrolyte and organic polymer electrolyte to be prone to the electrolytical lithium-air battery of miscible two-phase and lithium-metal battery all is to utilize the solid ceramic electrolyte as barrier film aqueous electrolyte and organic polymer electrolyte to be prone to miscible electrolyte for these two kinds to separate; But solid electrolyte film (like the LISICON film) can be corroded when contacting with strong basicity water-based electrolyte; In a single day as breaking; Can cause negative active core-shell material lithium, organic polymer electrolyte directly to contact with aqueous electrolyte, this can have a strong impact on the fail safe of said battery, has bigger potential safety hazard.So said barrier film or solid electrolyte film are separated mode and are faced quite difficulty at present, need to seek in addition solution route.
The immiscible two-phase electrolyte of research is " liquid/liquid " electrolyte (or being called " oil/water " two-phase electrolyte) the earliest.Though the contact of " liquid/liquid " interface is good, promptly on microcosmic, can reach the contact of molecule degree, " liquid/liquid " interface easy deformation does not have mechanical strength, is mainly used in laboratory research at present.Gu the electrolytical interface of the two-phase mechanical strength at " Gu/" interface is higher; But because solid-phase electrolyte self has rigidity to a certain degree; Shape and composition are difficult after the moulding changes; Do not reach the smooth, smooth of molecule degree on the microcosmic yet; So " Gu Gu/" interface is difficult for reaching the contact good state, promptly " Gu Gu/" interface is difficult in the contact that reaches the molecule degree on the microcosmic, is the two-phase electrolyte that the employed hydrogel electrolyte of Chinese patent/organogel electrolyte of ZL200110018250.9 is " Gu Gu/" interface like the patent No..See from principle; Just can make immiscible two-phase electrolyte system possess conductive capability as long as let ion on immiscible two kinds of electrolyte interfaces, flow freely; But in order to guarantee ion more swimmingly through the electrolyte boundary, two-phase electrolyte boundary should reach the contact of molecule degree; And during lithium-air battery work (in discharge process), LiOH in the aqueous electrolyte (lithium hydroxide) concentration can raise; Be prone to deposition, be unfavorable for the continuous operation of lithium-air battery, need constantly separate LiOH deposition (He P; Wang Y G, Zhou H S.Electrochem.Commun., 2010; 12:1686-1689), but when adopting the two-phase electrolyte at " solid/" interface, just must be in order to separate the LiOH deposition with the aqueous gel electrolyte dismounting in the two-phase electrolyte at " Gu Gu/" interface; Lithium-air battery must be out of service like this (promptly having a power failure), can influence the continuous operation of lithium-air battery; So " Gu Gu/" the two-phase electrolyte at interface is applicable to the lithium-air battery of service intermittent, but is not suitable for the lithium-air battery of continuity work.And precipitation form is LiOHH
2O (J.Christensen, P.Albertus, R.S.Sanchez-Carrera, T.Lohmann; B.Kozinsky, R.Liedtke, JAhmed, A.Kojica; Journal of The Electrochemical Society, 2012,159 (2), R1-R30); Water content in the gel state electrolyte is lower, so, forming LiOHH
2Can absorb the water in the hydrogel electrolyte in a large number during the O deposition, unfavorable to the electrolytical stability of hydrogel.Also increased the problem of the two-phase electrolyte operation at " Gu Gu/" interface.
All there is defective in the electrolytical mode of two-phase at the mode that the solid barrier film is cut apart described in the above-mentioned prior art, " Gu Gu/" interface; These defectives are unfavorable factors to lithium-air battery and the lithium-metal battery that uses it; Therefore demand opening up a kind of two-phase electrolyte urgently, to solve the electrolytical defective of above-mentioned two-phase.
Summary of the invention
For solving the electrolytical defective of two-phase in the prior art; One of the object of the invention is to provide a kind of immiscible " water/polymer " two-phase electrolyte; Said two-phase electrolyte is made up of aqueous electrolyte and hydrophobic organic polymer electrolyte, and both constitute immiscible two-phase electrolyte; Can form stable, interface clearly between the two-phase, need not to separate with macromolecular material barrier film or solid electrolyte membrane; And, help improving mechanical stability, alkali resistance and the acid resistance at said interface because the hydrophobic organic polymer electrolyte is alkali resistance, the acid resistance material with certain rigid, applicability widely can be arranged.
Two of the object of the invention is to provide a kind of battery, and the electrolyte of said battery is a kind of immiscible " water/polymer " provided by the present invention two-phase electrolyte, and said battery can be lithium-air battery or lithium-metal battery; Wherein, said lithium-metal battery can be lithium-copper battery or lithium-nickel-based battery.
The objective of the invention is to realize through following technical scheme.
A kind of immiscible " water/polymer " two-phase electrolyte; Said electrolyte is made up of aqueous electrolyte and hydrophobic organic polymer electrolyte, and is immiscible and form stable, interface clearly between aqueous electrolyte and the hydrophobic organic polymer electrolyte.
Wherein, said aqueous electrolyte is sulfuric acid (H
2SO
4) aqueous solution, perchloric acid (HClO
4) aqueous solution, potassium sulfate (K
2SO
4) aqueous solution, sodium sulphate (Na
2SO
4) aqueous solution, potassium hydroxide (KOH) aqueous solution, NaOH (NaOH) aqueous solution or copper sulphate (CuSO
4) aqueous solution; Solute in the preferred said aqueous electrolyte is analyzes pure chemistry reagent, and preferred solvent is three distilled water.
Said hydrophobic organic polymer electrolyte is made up of hydrophobic polymer, support salt and hydrophobic organic solvent; Wherein, said hydrophobic polymer is polymethyl methacrylate or polyacrylonitrile; Support that salt is the common employed lithium salts of this area battery, confirm the concrete kind of forming according to applied battery, preferred lithium perchlorate, di-oxalate lithium borate or LiBF4 support that the concentration of lithium ion in the salt is 0.5～1mol/L; Hydrophobic organic solvent is wherein one or both a mixture of propene carbonate, dimethyl carbonate or diethyl carbonate; In said hydrophobic organic polymer electrolyte oeverall quality is 100%, and the mass percent of said hydrophobic polymer is 5～30%, is preferably 10～20%.
A kind of battery, the electrolyte that said battery uses is a kind of immiscible " water/polymer " of the present invention two-phase electrolyte, said battery can be lithium-air battery or lithium-metal battery; Wherein, said lithium-metal battery can be lithium-copper battery or lithium-nickel-based battery.
Specifically, a kind of battery, said battery is made up of electrolyte, positive pole, negative pole and lead; Wherein, said electrolyte is a kind of immiscible " water/polymer " of the present invention two-phase electrolyte, and wherein aqueous electrolyte is used for positive pole, and the hydrophobic organic polymer electrolyte is used for negative pole; Said just very air electrode, metallic copper electrode or nickel oxide electrode are arranged in aqueous electrolyte; Said negative pole is a metal lithium electrode, is embedded in the hydrophobic organic polymer electrolyte; External circuit is communicated with through lead and load (electrical equipment) between positive pole and the negative pole, and conductor part is used wrapped with insulation, and the lead two ends are exposed metal and are fixedly connected with negative pole with anodal respectively; Interior circuit is communicated with through said immiscible " water/polymer " two-phase electrolyte, constitutes the closed-loop path.
Wherein, When air electrode just very; Said battery is a lithium-air battery; Aqueous electrolyte is aqueous sulfuric acid, high chloro acid solution, potassium sulfate solution, aqueous sodium persulfate solution, potassium hydroxide aqueous solution or sodium hydrate aqueous solution, and the acid-base value of said aqueous electrolyte (being hydrogen ion/hydroxide ion concentration) is H
+=2mol/L～OH
-=6mol/L; Said air electrode is the air electrode that lithium-air battery adopts usually, and catalyst is that carbon carries platinum black, and preferred operational analysis purity oxygen of air electrode or process purify the air of (dedusting, removing carbon dioxide).
When metallic copper electrode just very, said battery is lithium-copper battery, and aqueous electrolyte solution is copper sulfate solution, and concentration can be 0.5～5mol/L; It is pure that the purity of preferred said metallic copper and copper sulphate is analysis.
When nickel oxide electrode just very, said battery is lithium-nickel-based battery, and aqueous electrolyte solution is potassium hydroxide aqueous solution, and preferred concentration is 6mol/L.
Beneficial effect
1. a kind of immiscible " water/polymer " provided by the present invention two-phase electrolyte, wherein hydrophobic organic polymer electrolyte self has suitable hydrophobicity, viscosity, conductivity and acid-base value tolerance level, thereby can tolerate from H
+=2mol/L is to OH
-The aqueous electrolyte of=6mol/L scope acid-base value, and form stable, interface clearly between the aqueous electrolyte; This interface is the functional areas of a kind of flexibility, water proof and oxygen barrier; Can replace rigid solid dielectric film of the prior art; Realize not mixing, keep the multiple effect that lithium anode is stable and ion freely transports each other with aqueous electrolyte, conductivity can reach 10
-4More than the S/cm, aqueous electrolyte contacts well with the hydrophobic organic polymer electrolyte, and said interface is with immiscible " liquid/liquid " and " Gu Gu/" the electrolytical advantage of interface two-phase;
2. a kind of immiscible " water/polymer " provided by the present invention two-phase electrolyte; Be applicable to continous way two-phase electrolytic cell; Need not when using the LiOH deposition that the electrolytical lithium-air battery of said two-phase produced in removing running out of service, can continuous operation;
3. a kind of immiscible " water/polymer " provided by the present invention two-phase electrolyte helps on the one hand multi-electrode material is more made up, and obtains the chemical power source of high-energy-density, high power density; On the other hand, because the flexible characteristic at said interface has been avoided the broken easily defective of solid rigidity dielectric film; Simultaneously, the technology of such compound mode and battery system and ripe at present phase transfer catalysis (PTC) industry, the technology of objectionable intermingling electrolyte solution electrochemical field can be used for reference each other, mutually promoted;
4. a kind of battery provided by the present invention; The electrolyte that said battery uses is a kind of immiscible " water/polymer " provided by the invention two-phase electrolyte; Wherein, The negative active core-shell material lithium is wrapped in the organic polymer electrolyte, can directly not contact with aqueous electrolyte, and fail safe is good; When said battery was lithium-air battery, the LiOH that in removing running, is produced need not out of service when precipitating, can continuous operation.
Description of drawings
Fig. 1 is the graph of a relation of polymethyl methacrylate mass percent and said electrolyte viscosity in the hydrophobic organic polymer electrolyte among the embodiment 2.
Fig. 2 is the graph of a relation of polymethyl methacrylate mass percent and said electrolytic conductivity in the hydrophobic organic polymer electrolyte among the embodiment 2.
Fig. 3 be among the embodiment 3 the platinum ultramicro disc electrode at the electrolytical cyclic voltammogram of hydrophobic organic polymer.
Fig. 4 is the steady-state current curve chart of oxygen electrochemical reduction on the platinum ultramicro disc electrode in the hydrophobic organic polymer electrolyte among the embodiment 3.
Fig. 5 is the complex impedance figure at " lithium/hydrophobic organic polymer electrolyte " interface among the embodiment 4.
Fig. 6 is " polymethyl methacrylate mass percent and lithium-air battery discharge behavior " graph of a relation in the embodiment 5 hydrophobic organic polymer electrolyte.
Fig. 7 is " acid-base value of aqueous electrolyte and lithium-air battery discharge behavior " graph of a relation among the embodiment 5.
Fig. 8 is " discharge current density and lithium-air battery discharge behavior " graph of a relation among the embodiment 5.
Fig. 9 is " polymethyl methacrylate mass percent and lithium-copper battery discharge behavior " graph of a relation in the embodiment 6 hydrophobic organic polymer electrolyte.
Figure 10 is " concentration of copper sulfate of aqueous electrolyte and the lithium-copper battery discharge behavior " graph of a relation among the embodiment 6.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is described further.
A kind of lithium-air battery, said battery is made up of electrolyte, positive pole, negative pole and lead; Wherein, Said electrolyte is a kind of immiscible " water/polymer " two-phase electrolyte; Form by aqueous electrolyte and hydrophobic organic polymer electrolyte, immiscible and form stable, interface clearly between aqueous electrolyte and the hydrophobic organic polymer electrolyte; Wherein, aqueous electrolyte is used for positive pole, and the hydrophobic organic polymer electrolyte is used for negative pole; Said just very air electrode is arranged in aqueous electrolyte; Said negative pole is a metal lithium electrode, is embedded in the hydrophobic organic polymer electrolyte; External circuit is communicated with lead and load (electrical equipment) between positive pole and the negative pole, and lead is used wrapped with insulation, and the lead two ends are exposed metal and are fixedly connected with negative pole with anodal respectively; Interior circuit is communicated with said immiscible " water/polymer " two-phase electrolyte, constitutes the closed-loop path.
Said hydrophobic organic polymer electrolyte obtains through polymethyl methacrylate and lithium perchlorate are dissolved in the propene carbonate, and the amount of substance concentration of lithium perchlorate is 0.5mol/L.
Said air electrode is catalyst for carrying the carbon black electrode of platinum through use a year platinum carbon black with commodity, and polyvinyl alcohol is a binding agent, and the commodity nickel foam is a collector, and the three is prepared by tablet press machine is compressed together, uses purifying air of dedusting and carbon dioxide.
A kind of lithium-copper battery, said battery is made up of electrolyte, positive pole, negative pole and lead; Wherein, Said electrolyte is a kind of immiscible " water/polymer " two-phase electrolyte; Form by aqueous electrolyte and hydrophobic organic polymer electrolyte, immiscible and form stable, interface clearly between aqueous electrolyte and the hydrophobic organic polymer electrolyte; Wherein, aqueous electrolyte is used for positive pole, and the hydrophobic organic polymer electrolyte is used for negative pole; Said just very metallic copper electrode is arranged in aqueous electrolyte; Said negative pole is a metal lithium electrode, is embedded in the hydrophobic organic polymer electrolyte; External circuit is communicated with lead and load (electrical equipment) between positive pole and the negative pole, and lead is used wrapped with insulation, and the lead two ends are exposed metal and are fixedly connected with negative pole with anodal respectively; Interior circuit is communicated with said immiscible " water/polymer " two-phase electrolyte, constitutes the closed-loop path.
Said aqueous electrolyte solution is copper sulfate solution.
Said hydrophobic organic polymer electrolyte obtains through polymethyl methacrylate and lithium perchlorate are dissolved in the propene carbonate, and the amount of substance concentration of lithium perchlorate is 0.5mol/L.
It is pure that the purity of said metallic copper and copper sulphate is analysis.
The hydrophobic organic polymer electrolyte that contains the polymethyl methacrylate of different quality percentage according to the preparation of the method described in the embodiment 1; Wherein, the amount of substance concentration of lithium perchlorate is 0.5mol/L, is 100% in the electrolytical quality of hydrophobic organic polymer, and the mass percent of polymethyl methacrylate is respectively 0%, 5%, 10%, 15%, 20%, 25% and 30%.
Adopt ac impedance technology to measure electrolytical viscosity of said hydrophobic organic polymer (σ) and conductivity (η); Go up the two platinum conductance electrodes of employing at CHI660A electrochemical workstation (Shanghai occasion China company) and measure, it is as depicted in figs. 1 and 2 to obtain the result.
Transverse axis among Fig. 1 is the mass percent concentration of polymethyl methacrylate in the hydrophobic organic polymer electrolyte (PMMA), is expressed as C
PMMA, unit is W/W%, and the longitudinal axis is a dynamic viscosity, and unit is mPas (centipoise second); Transverse axis among Fig. 1 is the mass percent concentration of polymethyl methacrylate in the hydrophobic organic polymer electrolyte, is expressed as C
PMMA, unit is W/W%, and the longitudinal axis is conductivity (σ), and unit is S/cm (west/centimetre).The result shows that when the mass percent of polymethyl methacrylate in the said hydrophobic organic polymer electrolyte was lower than 20%, the electrolytical viscosity rising of hydrophobic organic polymer amplitude was less, and conductivity descends slower; And when the polymethyl methacrylate mass percent was higher than 20%, the electrolytical viscosity rising of hydrophobic organic polymer amplitude was bigger, and conductivity descends very fast.
Adopt three-electrode system to measure electrolytical hydrophobicity of hydrophobic organic polymer and the oxygen barrier performance that embodiment 2 prepares respectively.Said three-electrode system prepares through following method:
Said hydrophobic organic polymer electrolyte is divided into two groups; One group is used for measuring hydrophobicity; Transfer in the glass electrolysis tank with after 22 ± 2 ℃ the steam-ladens, another group is used for measuring the oxygen barrier performance, transfers in the glass electrolysis tank afterwards with 22 ± 2 ℃ oxygen are saturated; Be that 25 microns platinum ultramicro disc electrode is that 0.5 millimeter silver (Ag) silk is that 0.5 millimeter Ti electrode is for to electrode as accurate reference electrode, diameter as work electrode, diameter with diameter in each electrolysis tank; Said three kinds of electrodes are positioned in the hydrophobic organic polymer electrolyte of said glass electrolysis tank and were not had, constitute three-electrode system, the measuring junction of three kinds of electrodes is connected on the CHI660A electrochemical workstation; Measure its electrochemical window respectively with the cyclic voltammetric technology; Wherein, the scanning potential range of hydrophobicity measurement group is that 0V arrives-2.6V, and scanning speed is 1 millivolt/second of degree; The scanning potential range of the steady-state current curve of the oxygen reduction of oxygen barrier performance measurement group is from 0V to-1.6V, 1 millivolt/second of sweep speed; Obtain result such as Fig. 3 and shown in Figure 4.Wherein, The coordinate longitudinal axis is an electric current; Transverse axis is the scanning electromotive force, the numeral of numerical value for obtaining with respect to the accurate reference electrode of Ag silk, and note is made E/V vs.Ag QRE; The mass percent of polymethyl methacrylate in the other numeral hydrophobic organic polymer electrolyte of every curve, the degree that increases from electric current is to judge electrolytical hydrophobicity of said hydrophobic organic polymer and oxygen barrier performance.
Curve among Fig. 3 shows mass percent and the said hydrophobic organic polymer electrolyte electrochemical window of polymethyl methacrylate, the relation of water content; Explanation increases with the mass percent of polymethyl methacrylate; Hydrophobic organic polymer electrolyte electrochemical window broadens, and the negative terminal electromotive force numerical value that mainly shows as electrochemical window is more negative.Simultaneously; Be metal platinum owing to measure the active electrode material of the ultramicro disc electrode that uses, metal platinum has very high activity to the electrochemical decomposition of water, says from electrochemical principle; The electromotive force numerical value of the electrochemical decomposition correspondence of generation water is negative more; Explain that then the water content in the hydrophobic organic polymer electrolyte is few more, and the size of current of corresponding water decomposition behind decomposition potential (being flex point value corresponding on the curve) is with the also regular variation of the variation of polymethyl methacrylate mass percent, so the increase with the polymethyl methacrylate mass percent also has been described; Water content progressively reduces in the hydrophobic organic polymer electrolyte, and promptly hydrophobic performance strengthens.
Curve among Fig. 4 shows the mass percent of polymethyl methacrylate and the relation of hydrophobic organic polymer electrolyte oxygen barrier performance; Explanation is with the increase of polymethyl methacrylate mass percent; The reduction current of oxygen in the hydrophobic organic polymer electrolyte progressively reduces; Show the increase with the polymethyl methacrylate mass percent, the hydrophobic organic polymer electrolyte progressively strengthens the barrier property of oxygen.Reason is; When electrode potential numerical value reaches a certain scope, be metal platinum owing to measure the active electrode material of the ultramicro disc electrode that uses, it is a kind of material of high catalytic activity that metal platinum is reacted for oxygen reduction; Reduction reaction can take place in oxygen on the platinum ultramicro disc electrode; Contained concentration of oxygen and diffusion velocity in the corresponding hydrophobic organic polymer electrolyte of the electric current of reaction, when oxygen concentration is low more, diffusion velocity is slow more, then electric current is more little.The reduction of concentration of oxygen and diffusion velocity in the presentation of results hydrophobic organic polymer electrolyte of curve representation, promptly with the increase of polymethyl methacrylate mass percent, the hydrophobic organic polymer electrolyte progressively strengthens the barrier property of oxygen.
Embodiment 4
Adopt stability and the said hydrophobic organic polymer electrolytical hydrophobicity of symmetrical button cell test lithium metal in the hydrophobic organic polymer electrolyte that embodiment 2 prepares.The preparation method of said symmetrical button cell is following: use the celgard2300 barrier film that size, diameters such as two are separated as the lithium metal disk of 16mm; Place the stainless steel casing (commercial 2025 types) of button cell; Said hydrophobic organic polymer electrolyte is poured in the stainless steel casing respectively; Treat that the hydrophobic organic polymer electrolyte soaks into the back encapsulation with barrier film, lithium metal disk, obtains symmetrical button cell; All operations in the above-mentioned preparation process is all accomplished in the argon gas glove box; Encapsulation was left standstill 24 hours after accomplishing, and guaranteed that the hydrophobic organic polymer electrolyte fully soaks into barrier film and lithium metal.The symmetrical button cell that assembles is placed the measurement of carrying out AC impedance on the CHI660A electrochemical workstation, as shown in Figure 5.
Among Fig. 5, the other numeral of each curve is the mass percent of polymethyl methacrylate in the hydrophobic organic polymer electrolyte; Circular arc is the capacitive reactance arc, the appearance of this characteristic, show lithium metal can be in the hydrophobic organic polymer electrolyte stable existence;
Value corresponding is represented the impedance component of impedance on real axis at " lithium/hydrophobic organic polymer electrolyte " interface on the transverse axis, and the unit of transverse axis is ohm, is expressed as Z/ohm; The longitudinal axis is represented the impedance component of impedance on the imaginary axis at " lithium/hydrophobic organic polymer electrolyte " interface, and the unit of the longitudinal axis is ohm, Biao Shi Wei – Z "/ohm.Numerical value on the real axis is big more, and the degree of stability of expression lithium metal in the hydrophobic organic polymer electrolyte is high more, shows that also the content of water, oxygen in the hydrophobic organic polymer electrolyte is few more, and this is very crucial to the stable of lithium metal; Numerical value on the longitudinal axis and " lithium/hydrophobic organic polymer electrolyte " adion at interface, the absorption behavior of molecule are relevant.
Measure the influence of the lithium-air battery that acid-base value (being hydrogen ion/hydroxide ion concentration) and the discharge current density of mass percent, the aqueous electrolyte of polymethyl methacrylate in the hydrophobic organic polymer electrolyte that embodiment 2 prepares prepare embodiment 1 with discharge test.Discharge test discharges and recharges on the instrument (Wuhan Li Xing company) at Land and carries out.
(1) mass percent of polymethyl methacrylate is to the lithium-air battery Effect on Performance
The aqueous electrolyte of lithium-air battery is the aqueous sulfuric acid of 0.5mol/L.The lead of said lithium-air battery is connected Land to discharge and recharge on the appearance and measures.Measurement procedure is following: in aqueous sulfuric acid, slowly feed purifying air of dedusting and carbon dioxide; Change the hydrophobic organic polymer electrolyte that contains different quality percentage polymethyl methacrylate for preparing the embodiment 2 successively from 0%～30%; Obtain a series of lithium-air batteries, investigate of the influence of the mass percent of polymethyl methacrylate the hydrophobic organic polymer electrolyte said lithium-air battery from the behavior of these a series of lithium-air batteries.Measurement result is as shown in Figure 6.
Among Fig. 6, transverse axis calculates with the weight of lithium metal for the specific capacity (unit: MAH/gram is designated as mAh/g) of discharge, the influence of lithium-air battery being discharged with the mass percent of investigating polymethyl methacrylate in the hydrophobic organic polymer electrolyte; The longitudinal axis is the terminal voltage (unit: volt is designated as V) of lithium-air battery.Fig. 6 result shows; When the mass percent of polymethyl methacrylate is 10%～20%; The mechanical stability at said hydrophobic organic polymer electrolyte and two-phase electrolytical " water/polymer " interface is all better, can stop penetrating of oxygen, water, effectively protects the stable discharging of lithium metal; So, discharge time and capacity significantly raise (being significantly to increase discharge time).The discharge capacity of transverse axis is that the weight with lithium metal converts; As everyone knows, the theoretical capacity of lithium metal is 3860mAh/g, so the present embodiment presentation of results; Mass percent at polymethyl methacrylate is 10%～20% o'clock; The performance of said lithium-air battery is best, has both helped the stability that the guarantee fund belongs to lithium, helps guaranteeing the infiltration degree of lithium metal in hydrophobicity machine organic polymer electrolyte again.
(2) acid-base value of aqueous electrolyte is to the influence of lithium-air battery
Be the influence of the acid-base value of investigating aqueous electrolyte to said lithium-air battery discharge performance; The mass percent of selecting polymethyl methacrylate for use is 10% hydrophobic organic polymer electrolyte; Aqueous electrolyte is respectively 0.5mol/L aqueous sulfuric acid, 0.5mol/L aqueous sodium persulfate solution and 1mol/L sodium hydrate aqueous solution; The behavior measure that discharges respectively, measurement result is as shown in Figure 7.
The transverse axis of Fig. 7 is the specific discharge capacity (unit: MAH/gram is designated as mAh/g) of said lithium-air battery, calculates with the weight of lithium metal, with the influence to said lithium-air battery discharge of the acid-base value (hydrogen ion concentration) of investigating aqueous electrolyte; The longitudinal axis is the terminal voltage (unit: volt is designated as V) of said lithium-air battery.Hydrogen ion is high more in Fig. 7 display result explanation aqueous electrolyte, and the discharge voltage of lithium-air battery is also high more, and hydroxide ion is high more in the aqueous electrolyte, and the discharge voltage of lithium-air battery is also low more.
(3) discharge current density is to the influence of lithium-air battery
For investigating the influence of discharge current density to said lithium-air battery, the mass percent of selecting polymethyl methacrylate for use is 10% hydrophobic organic polymer electrolyte, and aqueous electrolyte is the aqueous sulfuric acid of 0.5mol/L; Current density discharges and recharges appearance control with Land, carries out discharge measuring, and measurement result is as shown in Figure 8.
The transverse axis of Fig. 8 is the specific discharge capacity (unit: MAH/gram is designated as mAh/g) of said lithium-air battery, calculates with the weight of lithium metal, to investigate the influence of discharge current density to said lithium-air battery discharge; The longitudinal axis is the terminal voltage (unit: volt is designated as V) of said lithium-air battery.The result shows that the discharging current of lithium-air battery is big more, and then discharge voltage is low more.
Embodiment 6
Measure mass percent, the copper ion concentration of aqueous electrolyte and the influence of lithium-copper battery that discharge current density prepares embodiment 1 of polymethyl methacrylate in the hydrophobic organic polymer electrolyte that embodiment 2 prepares with discharge test; Discharge test discharges and recharges on the instrument (Wuhan Li Xing company) at Land and carries out.
(1) in the hydrophobic organic polymer electrolyte polymethyl methacrylate mass percent to the influence of lithium-copper battery
The aqueous electrolyte of lithium-copper battery is the copper sulfate solution of 1.5mol/L.The lead of said lithium-copper battery is connected Land discharges and recharges and carry out discharge measuring on the appearance, it is as shown in Figure 9 to obtain the result.Wherein, The transverse axis of Fig. 9 is said lithium-copper battery discharge specific capacity (unit: MAH/gram; Be designated as mAh/g), calculate with the weight of lithium metal, with the influence of the mass percent of investigating polymethyl methacrylate in the hydrophobic organic polymer electrolyte lithium-copper battery discharge; The longitudinal axis is the terminal voltage (unit: volt is designated as V) of said lithium-copper battery.
Measurement procedure is following: change the hydrophobic organic polymer electrolyte that contains different quality percentage polymethyl methacrylate for preparing the embodiment 2 successively from 0%～30% during measurement, obtain in the hydrophobic organic polymer electrolyte polymethyl methacrylate mass percent to the impact effect of lithium-copper battery.The result shows that along with polymethyl methacrylate mass percent in the hydrophobic organic polymer electrolyte increases, the discharge voltage of lithium-copper battery progressively reduces, but increases earlier discharge time, and shorten the back.Reason is consistent to the reason of lithium-air battery discharge behavioral implications with the mass percent of polymethyl methacrylate.
(2) copper ion concentration in the aqueous electrolyte is to the influence of lithium-copper battery
Be the influence of the copper ion in the investigation aqueous electrolyte to said lithium-copper battery; Use polymethyl methacrylate mass percent is 10% hydrophobic organic polymer electrolyte; Aqueous electrolyte is respectively the copper sulfate solution of 0.5mol/L, 1.0mol/L and 1.5mol/L; Discharge and recharge with Land and to carry out discharge measuring on the appearance, measurement result is shown in figure 10.The transverse axis of Figure 10 is the specific capacity (unit: MAH/gram is designated as mAh/g) of said lithium-copper battery discharge, calculates with the weight of lithium metal, to investigate in the aqueous electrolyte copper ion concentration to the influence of said lithium-copper battery discharge; The longitudinal axis is the terminal voltage (unit: volt is designated as V) of said lithium-copper battery.Presentation of results is along with the copper ion concentration in the aqueous electrolyte increases, and the discharge voltage of lithium-copper battery raises, otherwise, then reduce.
(c) discharge current density is to the influence of lithium-copper battery
Rule between lithium-copper discharge capacity of the cell and the discharge current density and lithium-air battery similar.
The present invention includes but be not limited to above embodiment, every any replacement or local improvement of being equal to of under spirit of the present invention and principle, carrying out all will be regarded as within protection scope of the present invention.
Claims (10)
1. immiscible " water/polymer " two-phase electrolyte; It is characterized in that: said electrolyte is made up of aqueous electrolyte and hydrophobic organic polymer electrolyte, and is immiscible and form stable, interface clearly between aqueous electrolyte and the hydrophobic organic polymer electrolyte;
Wherein, said aqueous electrolyte is aqueous sulfuric acid, high chloro acid solution, potassium sulfate solution, aqueous sodium persulfate solution, potassium hydroxide aqueous solution, sodium hydrate aqueous solution or copper sulfate solution;
Said hydrophobic organic polymer electrolyte is made up of hydrophobic polymer, support salt and hydrophobic organic solvent; Wherein, said hydrophobic polymer is polymethyl methacrylate or polyacrylonitrile; Support that salt is the common employed lithium salts of field of batteries, the concentration of lithium ion is 0.5～1mol/L; Hydrophobic organic solvent is wherein one or both a mixture of propene carbonate, dimethyl carbonate or diethyl carbonate; In said hydrophobic organic polymer electrolyte oeverall quality is 100%, and the mass percent of said hydrophobic polymer is 5～30%.
2. a kind of immiscible " water/polymer " according to claim 1 two-phase electrolyte is characterized in that: the various solutes in the said aqueous electrolyte are analyzes pure chemistry reagent, and solvent is three distilled water.
3. a kind of immiscible " water/polymer " according to claim 1 two-phase electrolyte, it is characterized in that: support salt is lithium perchlorate, di-oxalate lithium borate or LiBF4.
4. a kind of immiscible " water/polymer " according to claim 1 two-phase electrolyte, it is characterized in that: in said hydrophobic organic polymer electrolyte oeverall quality is 100%, and the mass percent of said hydrophobic polymer is 10～20%.
5. battery, it is characterized in that: the electrolyte that said battery uses is each described a kind of immiscible " water/polymer " two-phase electrolyte of claim 1～4.
6. a kind of battery according to claim 5 is characterized in that: said battery is lithium-air battery or lithium-metal battery.
7. a kind of battery according to claim 6 is characterized in that: said lithium-metal battery is lithium-copper battery or lithium-nickel-based battery.
8. a kind of battery according to claim 7 is characterized in that: said battery is made up of electrolyte, positive pole, negative pole and lead; Wherein, aqueous electrolyte is used for positive pole, and the hydrophobic organic polymer electrolyte is used for negative pole; Said just very air electrode, metallic copper electrode or nickel oxide electrode are arranged in aqueous electrolyte; Said negative pole is a metal lithium electrode, is embedded in the hydrophobic organic polymer electrolyte; External circuit is communicated with through lead and applied load between positive pole and the negative pole, and lead is used wrapped with insulation, and the lead two ends are exposed metal and are fixedly connected with negative pole with anodal respectively; Interior circuit is communicated with through electrolyte, constitutes the closed-loop path;
When air electrode just very; Said battery is a lithium-air battery; Aqueous electrolyte is aqueous sulfuric acid, high chloro acid solution, potassium sulfate solution, aqueous sodium persulfate solution, potassium hydroxide aqueous solution or sodium hydrate aqueous solution, and the acid-base value of said aqueous electrolyte is H
+=2mol/L～OH
-=6mol/L; Said air electrode is the air electrode that lithium-air battery adopts usually, and catalyst is that carbon carries platinum black, air electrode operational analysis purity oxygen or the air that purifies through dedusting, removing carbon dioxide;
When metallic copper electrode just very, said battery is lithium-copper battery, and aqueous electrolyte solution is copper sulfate solution, and concentration is 0.5～5mol/L;
When nickel oxide electrode just very, said battery is lithium-nickel-based battery, and aqueous electrolyte solution is potassium hydroxide aqueous solution.
9. a kind of battery according to claim 8 is characterized in that: it is pure that the purity of said metallic copper and copper sulphate is analysis.
10. a kind of battery according to claim 8 is characterized in that: when nickel oxide electrode just very, said battery is lithium-nickel-based battery, and aqueous electrolyte solution is the potassium hydroxide aqueous solution of 6mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101647467A CN102709624A (en) | 2012-05-24 | 2012-05-24 | Immiscible water/polymer two-phase electrolyte and battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101647467A CN102709624A (en) | 2012-05-24 | 2012-05-24 | Immiscible water/polymer two-phase electrolyte and battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102709624A true CN102709624A (en) | 2012-10-03 |
Family
ID=46902255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101647467A Pending CN102709624A (en) | 2012-05-24 | 2012-05-24 | Immiscible water/polymer two-phase electrolyte and battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102709624A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682510A (en) * | 2013-12-03 | 2014-03-26 | 广东电网公司电力科学研究院 | Electrolyte used for waste lithium battery discharge, and waste lithium battery discharge method |
| CN106298250A (en) * | 2016-10-31 | 2017-01-04 | 中南大学 | A kind of solid lithium ion super capacitor hybrid battery |
| CN111342117A (en) * | 2020-02-02 | 2020-06-26 | 江苏大学 | Super-hydrophobic solid electrolyte of lithium-air battery and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1680482A (en) * | 2005-02-04 | 2005-10-12 | 武汉大学 | Non-aqueous/aqueous two-phase gel electrolyte, preparation and battery thereof |
| CN101960664A (en) * | 2008-12-25 | 2011-01-26 | 丰田自动车株式会社 | Lithium air battery |
-
2012
- 2012-05-24 CN CN2012101647467A patent/CN102709624A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1680482A (en) * | 2005-02-04 | 2005-10-12 | 武汉大学 | Non-aqueous/aqueous two-phase gel electrolyte, preparation and battery thereof |
| CN101960664A (en) * | 2008-12-25 | 2011-01-26 | 丰田自动车株式会社 | Lithium air battery |
Non-Patent Citations (2)
| Title |
|---|
| G.GIRISHKUMAR,ET AL.: "Lithium-Air Battery:Promise and challenges", 《THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS》, 2 July 2010 (2010-07-02) * |
| YONGGANG WANG,ET AL.: "A lithium-air battery with a potential to continuously reduce O2 from air for delivering energy", 《JOURNAL OF POWER SOURCES》, vol. 195, 18 July 2009 (2009-07-18) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682510A (en) * | 2013-12-03 | 2014-03-26 | 广东电网公司电力科学研究院 | Electrolyte used for waste lithium battery discharge, and waste lithium battery discharge method |
| CN103682510B (en) * | 2013-12-03 | 2015-11-18 | 广东电网公司电力科学研究院 | For electrolyte and the charging method of waste lithium cell electric discharge |
| CN106298250A (en) * | 2016-10-31 | 2017-01-04 | 中南大学 | A kind of solid lithium ion super capacitor hybrid battery |
| CN111342117A (en) * | 2020-02-02 | 2020-06-26 | 江苏大学 | Super-hydrophobic solid electrolyte of lithium-air battery and preparation method thereof |
| CN111342117B (en) * | 2020-02-02 | 2022-10-28 | 江苏大学 | Super-hydrophobic solid electrolyte of lithium-air battery and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Imanishi et al. | Rechargeable lithium–air batteries: characteristics and prospects | |
| Harting et al. | Zinc-air batteries: prospects and challenges for future improvement | |
| CN1320674C (en) | Electrolyte additive for non-aqueous electrochemical cells | |
| CN102315473A (en) | Lithium ion flow redox battery | |
| JP6672691B2 (en) | Lithium ion capacitor | |
| CN202259549U (en) | Lithium ion flow battery | |
| KR20150018527A (en) | System comprising accumulators and air-aluminium batteries | |
| CN103069626A (en) | Liquid air electrode for metal-air battery and metal-air battery provided with same | |
| JP2016122650A (en) | All-solid metal-metal battery | |
| CN107181023A (en) | Non-aqueous lithium-air battery | |
| Lin et al. | O2/O2–Crossover-and Dendrite-Free Hybrid Solid-State Na–O2 Batteries | |
| CN107910195A (en) | A kind of hybrid super capacitor | |
| JP2018532224A (en) | Semi-solid flow Li / O2 battery | |
| CN106972192A (en) | For the method and electrolytic cell device, lithium-ion energy storage device of the prefabricated lithium of lithium-ion energy storage device negative pole | |
| CN102714339A (en) | Lithium air cell | |
| CN101840784A (en) | Electrolyte for super capacitor and super capacitor | |
| CN106067387B (en) | Lithium ion capacitor | |
| CN105206856A (en) | Novel lithium ion flow cell | |
| CN102709624A (en) | Immiscible water/polymer two-phase electrolyte and battery | |
| CN107275721A (en) | A kind of organic/water mixed stocker sodium air cell based on acidic electrolysis bath | |
| CN109037789A (en) | A kind of lithium aluminium double ion rechargeable battery | |
| CN104425856A (en) | Lithium-air battery and positive electrode | |
| US9954229B2 (en) | Electrolyte for stable cycling of high-energy lithium sulfur redox flow batteries | |
| CN103931049B (en) | aqueous electrolyte for lithium-air battery | |
| JP2003331912A (en) | Lithium ion conductive solid electrolyte composite body, and lithium cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121003 |