CN105047933A - Rechargeable quinone-manganese oxide aqueous battery - Google Patents
Rechargeable quinone-manganese oxide aqueous battery Download PDFInfo
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- CN105047933A CN105047933A CN201510547177.8A CN201510547177A CN105047933A CN 105047933 A CN105047933 A CN 105047933A CN 201510547177 A CN201510547177 A CN 201510547177A CN 105047933 A CN105047933 A CN 105047933A
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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Abstract
The invention relates to a rechargeable quinone-manganese oxide aqueous battery. The positive electrode of the rechargeable quinone-manganese oxide aqueous battery adopts an embedded compound to/from which a lithium ion and a zinc ion can be jointly inserted/extracted, the cathode adopts a quinone compound taking benzoquinone/multi-quinone with an aroma cyclic structure as an electrochemical oxidation reaction point, an electrolyte is a liquid-state or get-state material which takes a lithium salt and a zinc salt as a solvent and water as solution and has ionic conductivity, more than one kind of ions are involved in transferring between two poles during charging and discharging, therefore, an electrode structure is stabilized, the cyclic life of the rechargeable aqueous battery is prolonged, and moreover, the rechargeable quinone-manganese oxide aqueous battery has the characteristics of safety, low cost, environment friendliness, overcharging and over-discharging resistance, and is particularly suitable for the field of energy storage at a large scale.
Description
Technical field
The present invention relates to a kind of quinone-manganese oxide lithium water system battery filled, belong to the secondary cell field that can fill, also belong to technical field of energy material.
Background technology
For adapting to the energy storage demand of renewable generation of electricity by new energy and structure intelligent grid, in the urgent need to development long-life, low cost, safety and eco-friendly chemical energy storage battery system.Existing chemical energy storage battery mainly contains the lithium ion battery etc. of lead-acid battery, Ni-MH battery, flow battery and organic media.But for scale energy storage, do not have a kind of energy storage system can meet the requirement of scale energy storage completely so far.Lead-acid battery specific energy is lower, and the life-span is shorter, and containing toxic element.Ni-MH battery and flow battery valency expensive, competitiveness improve limited space.Though the low capacity lithium ion battery of organic media has possessed good conditions for sports industry, for scale energy storage, because of the problem that fail safe and cost remain high, limit the application of large-scale organolithium ion battery in energy storage.
For this reason, in recent years, safety, inexpensive aquo-lithium ion battery receive much attention, and its electrode material is generally introduced in conjunction with the electrolytical feature of water system organic lithium ion battery material and improved.In numerous anode material for lithium-ion batteries, spinel-type LiMn
2o
4have promoter manganese to enrich, environmental friendliness, low price, invertibity and conductivity better, become the positive electrode of aquo-lithium ion battery most application prospect.But, spinelle LiMn
2o
4for lower (the theoretical capacity 148mAhg of energy density during stoichiometric proportion
-1, actual discharge capacity 100 ~ 120mAhg
-1), Jahn-Teller distortion can occur in charge and discharge process, and disproportionated reaction can occur material in the electrolytic solution and Mn dissolves, cause capacitance loss serious, cycle performance is poor.Spinelle LiMn
2o
4for aquo-lithium ion battery, due to polar water molecules effect and analyse the impact of oxygen side reaction, capacity fade problem exists and more outstanding equally.
So far, aquo-lithium ion battery negative material adopts inorganic oxide material mostly, as VO
2, LiV
3o
8, TiO
2, V
2o
3, Na
2v
6o
160.14H
2o nano wire, H
2v
3o
8, TiP
2o
7and LiTi
2(PO
4)
3deng.Compared with aquo-lithium ion battery positive electrode, by oxygen in air and solvent water mitigation, negative material charge and discharge cycles is all no more than 200 times, and capacity attenuation is fast, and cyclical stability is more difficult to ensure.
Compared with inorganic material, organic electrodes material has the advantages such as theoretical specific capacity high, cheap (not relating to expensive element), reusable edible and height can design, and high temperature sintering conventional in not needing inorganic lithium ion intercalation materials to prepare, carbon discharge capacity is low.In addition organic substance is by being polymerized the stability improving material further, and therefore organic electrodes material is the ergastic substances that a class has wide application prospect.Organic quinones, in electrochemical reaction process, has good structural stability, is expected to develop into the competitive lithium secondary battery electrode material of a class.The theoretical capacity of organic quinones polymer is high (>400mAh/g), and average working voltage is generally at 2.0-2.5V (vs.Li/Li
+), and in molecular level design, by the approach such as In-situ reaction of polymerization, electric conducting material, improve conductivity and the cyclical stability of material; Compared with common inorganic material, organic quinones polymer performance room for promotion is very large, has the potential application foreground for aquo-lithium ion battery negative material.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, there is provided a kind of high-energy-density, high power density, than cost, environmental protection with long-lifely fill quinone-manganese oxide lithium water system energy-storage battery, to overcome the problem that existing aquo-lithium ion battery specific capacity is low, cycle life is short (particularly under low range).
For solving the problems of the technologies described above, the present invention takes following technical scheme
A kind of quinone-manganese oxide lithium water system battery filled, by cathode film, negative electrode film, marginal barrier film and contain polyvalent cation and the electrolyte solution with ionic conductivity forms, the inlaid scheme that described cathode film adopts lithium ion and zinc ion to embed altogether/deviate from; Described negative electrode film adopts the benzoquinones with aromatic shape structure or many quinones to be the quinones in electrochemical redox reaction site; Described electrolyte solution is with lithium salts, zinc salt for solute, and water is solvent and has liquid state or the gel state material of ionic conductivity.
Particularly, described cathode film is manganese oxide lithium compound, and the general formula of described manganese oxide lithium compound is Li
xmn
2o
y(43x32,53y34), wherein, adopt cobalt, chromium, nickel, titanium, vanadium, one or more in iron replace described in manganese oxide lithium compound in part manganese, one or more the addition in described cobalt, chromium, nickel, titanium, vanadium, iron accounts for 0 ~ 15mol% of manganese in described manganese oxide lithium compound; Adopt sodium, potassium, magnesium, calcium, zinc, one or more in copper replace described in manganese oxide lithium compound in part lithium, one or more the addition in described sodium, potassium, magnesium, calcium, zinc, copper accounts for 0 ~ 15mol% of lithium in described manganese oxide lithium compound; Adopt in fluorine root, phosphate radical, borate, silicate one or more replace described in manganese oxide lithium compound in part oxygen, one or more the addition in described fluorine root, phosphate radical, borate, silicate accounts for 0 ~ 5mol% of oxygen in described manganese oxide lithium compound.
Particularly, the collector material of described cathode film, negative electrode film is independently for being selected from the porous of one or more metal or alloy in copper, nickel, molybdenum, Stainless Steel, titanium, netted, thin-film material.
Particularly, described cathode film and described negative electrode film are added with conductive agent and binding agent independently, described conductive agent is conductive carbon powder or sub-titanium oxide or both mixtures, and described adhesive is polytetrafluoroethylene, Kynoar, phenolic resins, polyurethane, epoxy resin, polyether resin, latex rubber or their mixture.
Particularly, when being added with described conductive agent and described binding agent in described cathode film, the addition of described conductive agent is less than 30% of described cathode film gross mass; The addition of described binding agent is less than 20% of described cathode film gross mass;
When being added with described conductive agent and described binding agent in described negative electrode film, the addition of described conductive agent is less than 30% of described negative electrode film gross mass; The addition of described binding agent is less than 20% of described negative electrode film gross mass.
Particularly, also containing cation salt form additive in described electrolyte solution, wherein, described cation salt form additive is one or more in sodium salt, magnesium salts, calcium salt, strontium salt, barium salt, titanium salt, sylvite, rubidium salt, cesium salt, manganese salt, cobalt salt, nickel salt, mantoquita, aluminium salt, gallium salt and indium salt, described cation salt form additive level accounts for 0.01 ~ 20% of the total concentration of described cation salt form additive, described lithium salts and described zinc salt, the concentration of lithium salts is 0.02 ~ 5 mol/L, and zinc salt concentration is 0.05 ~ 3 mol/L.
Particularly, described quinones is the quinones compound being directly connected by C-C key or being formed with high conductivity material In-situ reaction in the course of the polymerization process by atom N or the quinones polymer be connected by S atom or quinones monomer, described high conductivity material comprises material with carbon element and conducting polymer, described material with carbon element be selected from graphite, Graphene, acetylene black, mesophase spherule microballoon, vapour-phase pyrolysis carbon, carbon nano-tube, organic cracking carbon one or more; Described conducting polymer be selected from polyaniline, polypyrrole, polythiophene, Polyglycolic acid fibre, Polyglycolic acid fibre and polystyrolsulfon acid compound one or more.
Particularly, described cell shapes is takeup type cylinder type, laminated type square or coin shape, and the shell of described battery is organic plastics, metal material or metal organic composite material.
In the present invention, described barrier film can adopt the porous septum of existing battery, as the compound barrier film of glass fibre (AGM) barrier film, porous polypropylene barrier film, ceramic diaphragm and more than one barrier films.
The technology of preparing of former secondary cell is all applicable to this water system rechargeable type quinone-manganese oxide lithium battery, comprises preparation technology's (batch mixing, press mold, film, slurry etc.) of electrode, and fills with the technique such as liquid and sealing.
The present invention propose can the basic functional principle of water-filling system battery as follows: in battery initial charge process, lithium ion is deviate from from positive pole, by electrolyte, Lithium-ion embeding negative pole.In discharge process, lithium ion is deviate from from negative pole, by electrolyte, and Lithium-ion embeding positive pole.In charge and discharge process afterwards, not only relate to lithium ion in two interelectrode transfers, also have the suction/desorption process of the bivalent cation such as zinc ion, magnesium ion in positive pole, thus improve battery specific capacity and cyclical stability.
Due to the enforcement of above technical scheme, the present invention compared with prior art has following advantage:
The present invention adopts the quinone of the composite structure of polymer architecture or polymer and high conductivity material to be negative pole, by polymerization and the compound with high conductivity material, improves the conductivity of quinone, reduces the decay of quinone capacity of negative plates simultaneously; In charge and discharge process, relate to the embedding of more than one cations in lithium manganese oxygen positive pole-deviate from and suction-desorption process, thus ensure that the cyclical stability of whole battery system.Novel filled quinone-manganese oxide lithium water system battery average working voltage at about 1.2V, and has high specific capacity and long cycle life, overcomes the problem that existing aquo-lithium ion battery specific capacity is on the low side, cycle performance is poor.Novel filled quinone-manganese oxide lithium water system battery has long circulation life, low cost, safety and eco-friendly feature, is specially adapted to extensive energy storage.
Accompanying drawing explanation
Fig. 1 is the charging and discharging curve of the quinone-manganese oxide lithium water system battery that can fill.
Embodiment
embodiment 1
With 1,5 diamino-anthraquinones are monomer, and obtained poly-1,5 diamino-anthraquinones of oxidation polymerization, obtain negative electrode active material.With LiMn
2o
4for initiation material, according to target product Li
3mn
2o
4the lithium source of chemistry metering ratio, add lithium carbonate, load in stainless steel jar mill and carry out ball milling mixing, by adding the polyvinyl alcohol granulation of 10% in mixed for ball milling powder stock, putting into ceramic boat, being placed in Muffle furnace, the constant temperature 12h when air atmosphere rises to 700 DEG C with 2 DEG C/min programming rate, then naturally cool to room temperature, product, after pulverizing, sieving, obtains rich lithium manganese lithium positive electrode active materials.Lithium for richness manganese lithium material and anthraquinone polymeric thing are mixed and made into slurry with acetylene black, polytetrafluoroethylene (PTFE) adhesive according to mass ratio 80:15:5 respectively, roll molded, be pressed on titanium net collector with the pressure of 20Mpa, make positive, negative electrode plate.With 1MLiCl+0.5MZnCl
2+ 0.2MMnCl
2the aqueous solution is electrolyte, and electrode slice puts into electrolyte vacuum immersion liquid 6 hours, is then that positive and negative electrode separated by barrier film with porous polypropylene film, is assembled into aqoue seconary battery.Battery is at 100mAg
-1under carry out constant current charge-discharge, discharge voltage range is 0.2-1.2V.Discharge capacity is 100mAhg first
-1, average discharge volt is 0.8V, and initial coulomb efficiency is 94%; Charge and discharge cycles 100 times, this capacity of negative plates attenuation rate is lower than 10%.
embodiment 2
Tetrachloroquinone and 10wt% carbon nano-tube are dissolved in nmp solvent, 160
0with Na under C
2s reacts the obtained poly-sulfo-benzoquinones of curable polymerisation and carbon mano-tube composite.This compound and acetylene black, PTFE adhesive are mixed and made into slurry according to mass ratio 80:15:5, roll molded, be pressed on stainless (steel) wire collector with the pressure of 20Mpa, under 393K, drying makes cathode pole piece in 6 hours in atmosphere.Be initiation material with manganese acetate, be dissolved in the water, according to target product Li
4mn
2o
4the lithium source of chemistry metering ratio, add lithium acetate and dissolve and form the aqueous solution, agitating heating dewaters, by adding the polyvinyl alcohol mixing granulation of 10% in the pressed powder after dewatering, putting into ceramic boat, being placed in Muffle furnace, the constant temperature 12h when air atmosphere rises to 700 DEG C with 2 DEG C/min programming rate, then naturally cool to room temperature, product, after pulverizing, sieving, obtains rich lithium manganese lithium positive electrode active materials.Lithium for richness manganese material and acetylene black, polytetrafluoroethylene (PTFE) adhesive are mixed and made into slurry according to mass ratio 85:10:5, roll molded, be pressed on stainless (steel) wire collector with the pressure of 20Mpa, make anode pole piece.With 1MLi
2sO
4+ 0.5MZnSO
4+ 0.2MMnSO
4the aqueous solution is electrolyte, and electrode slice puts into electrolyte vacuum immersion liquid 6 hours, is then that positive and negative electrode separated by barrier film with porous polypropylene film, is assembled into aqoue seconary battery.Battery is at 100mAg
-1under carry out constant current charge-discharge, discharge voltage range is 0.2-1.4V.Discharge capacity is 140mAhg first
-1, average discharge volt is 1.0V, and initial coulomb efficiency is 95%; Charge and discharge cycles 100 times, this capacity of negative plates attenuation rate is lower than 10%.
embodiment 3
By 2,5 dihydroxy benzoquinones are dissolved in acetic acid solvent, 80
0be polymerized obtained poly-2,5 dihydroxy benzoquinones with formolite reaction under C.This quinone polymer and acetylene black, PTFE adhesive are mixed and made into slurry according to mass ratio 55:40:5, roll molded, be pressed on stainless (steel) wire collector with the pressure of 20Mpa, under 393K, drying makes cathode pole piece in 6 hours in atmosphere.With MnO
2for initiation material, according to target product Li
2mn
2o
4the lithium source of chemistry metering ratio, add lithium carbonate and ball milling mixes, the polyvinyl alcohol mixing granulation of 10% is added in solid powder mixture, put into ceramic boat, be placed in Muffle furnace, the constant temperature 5h when air atmosphere rises to 500 DEG C with 5 DEG C/min programming rate, constant temperature 8h when then rising to 750 DEG C with 2 DEG C/min programming rate, naturally cool to room temperature, product, after pulverizing, sieving, obtains rich lithium manganese lithium positive electrode active materials.This rich lithium manganese material and acetylene black, polytetrafluoroethylene (PTFE) adhesive are mixed and made into slurry according to mass ratio 80:15:5, roll molded, be pressed on stainless (steel) wire collector with the pressure of 20Mpa, make anode pole piece.With 1MLi
2sO
4+ 0.5MZnSO
4+ 0.5MMnSO
4+ 0.2MMgSO
4the aqueous solution is electrolyte, and electrode slice puts into electrolyte vacuum immersion liquid 6 hours, is then that positive and negative electrode separated by barrier film with porous polypropylene film, is assembled into aqoue seconary battery.Battery is at 100mAg
-1under carry out constant current charge-discharge, discharge voltage range is 0.2-1.5V.Discharge capacity is 120mAhg first
-1, average discharge volt is 1.2V, and initial coulomb efficiency is 96%; Charge and discharge cycles 100 times, this capacity of negative plates attenuation rate is lower than 10%.
Comparative example 1
With quinones-tetrachloroquinone monomer for active material, mix according to the ratio of tetrachloroquinone with conductive agent acetylene black, PTFE adhesive mass ratio 55:40:5, roll and be pressed into pole piece, be compressed on stainless (steel) wire, make negative plate.With LiMn
2o
4for initiation material, according to target product Li
3mn
2o
4the lithium source of chemistry metering ratio, add lithium carbonate, load in stainless steel jar mill and carry out ball milling mixing, by adding the polyvinyl alcohol granulation of 10% in mixed for ball milling powder stock, putting into ceramic boat, being placed in Muffle furnace, the constant temperature 12h when air atmosphere rises to 700 DEG C with 2 DEG C/min programming rate, then naturally cool to room temperature, product, after pulverizing, sieving, obtains rich lithium manganese lithium positive electrode active materials.Then be that barrier film separates tetrachloroquinone negative pole and richness lithium manganese lithium positive pole with porous polypropylene film, inject electrolyte 1MLi
2sO
4+ 0.5MZnSO
4+ 0.2MMnSO
4water-soluble, be assembled into aqoue seconary battery.Battery is at 100mAg
-1under carry out constant current charge-discharge, discharge voltage range is 0.2-1.2V.Discharge capacity only has 20mAhg first
-1, average discharge volt is 0.8V, and initial coulomb efficiency is 70%; Charge and discharge cycles 50 times, this capacity attenuation rate 60%.
Comparative example 2
By soluble in water for non-quinones-pyrrole monomer, add surfactant sodium dodecyl base sodium sulfonate, ammonium persulfate is dissolved in deionized water simultaneously and is mixed with (NH
4)
2sO
4the aqueous solution, 0
0when C and constantly stirring, slowly drip (NH
4)
2sO
4the aqueous solution makes pyrroles's polymerization reaction 10 hours, by washed with de-ionized water precipitation, finally, by PPy dry 24h in 60 DEG C of vacuum drying chambers of polymerization, obtains polypyrrole.Take polypyrrole as active material, mix according to the ratio of active material with conductive agent acetylene black, PTFE adhesive mass ratio 80:15:5, roll and be pressed into pole piece and be compressed on stainless (steel) wire obtained negative plate.With MnO
2for initiation material, according to target product Li
2mn
2o
4the lithium source of chemistry metering ratio, add lithium carbonate and ball milling mixes, the polyvinyl alcohol mixing granulation of 10% is added in solid powder mixture, put into ceramic boat, be placed in Muffle furnace, the constant temperature 5h when air atmosphere rises to 500 DEG C with 5 DEG C/min programming rate, constant temperature 8h when then rising to 750 DEG C with 2 DEG C/min programming rate, naturally cool to room temperature, product, after pulverizing, sieving, obtains rich lithium manganese lithium positive electrode active materials.This rich lithium manganese material and acetylene black, polytetrafluoroethylene (PTFE) adhesive are mixed and made into slurry according to mass ratio 80:15:5, roll molded, be pressed on stainless (steel) wire collector with the pressure of 20Mpa, make anode pole piece.Then be that above-mentioned positive and negative plate separated by barrier film with porous polypropylene film, inject electrolyte 1MLi
2sO
4+ 0.5MZnSO
4+ 0.2MMnSO
4the aqueous solution, is assembled into aqoue seconary battery.Battery is at 100mAg
-1under carry out constant current charge-discharge, discharge voltage range is 0.2-1.2V.Discharge capacity only has 80mAhg first
-1, average discharge volt is 0.9V, and initial coulomb efficiency is 90%; Charge and discharge cycles 100 times, this capacity of negative plates attenuation rate 20%.
Above to invention has been detailed description; its object is to allow the personage being familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence change that all Spirit Essences according to the present invention are done or modification, all should be encompassed in protection scope of the present invention.
Claims (8)
1. the quinone that can fill-manganese oxide lithium water system battery, by cathode film, negative electrode film, marginal barrier film and contain polyvalent cation and the electrolyte solution with ionic conductivity forms, it is characterized in that: the inlaid scheme that described cathode film adopts lithium ion and zinc ion to embed altogether/deviate from; Described negative electrode film adopts the benzoquinones with aromatic shape structure or many quinones to be the quinones in electrochemical redox reaction site; Described electrolyte solution is with lithium salts, zinc salt for solute, and water is solvent and has liquid state or the gel state material of ionic conductivity.
2. quinone-manganese oxide lithium water system the battery filled according to claim 1, it is characterized in that: described cathode film is manganese oxide lithium compound, the general formula of described manganese oxide lithium compound is Li
xmn
2o
y(43x32,53y34), wherein, adopt cobalt, chromium, nickel, titanium, vanadium, one or more in iron replace described in manganese oxide lithium compound in part manganese, one or more the addition in described cobalt, chromium, nickel, titanium, vanadium, iron accounts for 0 ~ 15mol% of manganese in described manganese oxide lithium compound; Adopt sodium, potassium, magnesium, calcium, zinc, one or more in copper replace described in manganese oxide lithium compound in part lithium, one or more the addition in described sodium, potassium, magnesium, calcium, zinc, copper accounts for 0 ~ 15mol% of lithium in described manganese oxide lithium compound; Adopt in fluorine root, phosphate radical, borate, silicate one or more replace described in manganese oxide lithium compound in part oxygen, one or more the addition in described fluorine root, phosphate radical, borate, silicate accounts for 0 ~ 5mol% of oxygen in described manganese oxide lithium compound.
3. quinone-manganese oxide lithium water system the battery filled according to claim 1, is characterized in that: the collector material of described cathode film, negative electrode film is independently for being selected from the porous of one or more metal or alloy in copper, nickel, molybdenum, Stainless Steel, titanium, netted, thin-film material.
4. quinone-manganese oxide lithium water system the battery filled according to claim 1, it is characterized in that: described cathode film and described negative electrode film are added with conductive agent and binding agent independently, described conductive agent is conductive carbon powder or sub-titanium oxide or both mixtures, and described adhesive is polytetrafluoroethylene, Kynoar, phenolic resins, polyurethane, epoxy resin, polyether resin, latex rubber or their mixture.
5. quinone-manganese oxide lithium water system the battery filled according to claim 4, it is characterized in that: when being added with described conductive agent and described binding agent in described cathode film, the addition of described conductive agent is less than 30% of described cathode film gross mass; The addition of described binding agent is less than 20% of described cathode film gross mass;
When being added with described conductive agent and described binding agent in described negative electrode film, the addition of described conductive agent is less than 30% of described negative electrode film gross mass; The addition of described binding agent is less than 20% of described negative electrode film gross mass.
6. quinone-manganese oxide lithium water system the battery filled according to claim 1, it is characterized in that: also containing cation salt form additive in described electrolyte solution, wherein, described cation salt form additive is sodium salt, magnesium salts, calcium salt, strontium salt, barium salt, titanium salt, sylvite, rubidium salt, cesium salt, manganese salt, cobalt salt, nickel salt, mantoquita, aluminium salt, one or more in gallium salt and indium salt, described cation salt form additive level accounts for described cation salt form additive, 0.01 ~ 20% of the total concentration of described lithium salts and described zinc salt, the concentration of lithium salts is 0.02 ~ 5 mol/L, zinc salt concentration is 0.05 ~ 3 mol/L.
7. quinone-manganese oxide lithium water system the battery filled according to claim 1, it is characterized in that: described quinones is the quinones compound being directly connected by C-C key or being formed with high conductivity material In-situ reaction in the course of the polymerization process by atom N or the quinones polymer be connected by S atom or quinones monomer, described high conductivity material comprises material with carbon element and conducting polymer, described material with carbon element is for being selected from graphite, Graphene, acetylene black, mesophase spherule microballoon, vapour-phase pyrolysis carbon, carbon nano-tube, one or more in organic cracking carbon, described conducting polymer be selected from polyaniline, polypyrrole, polythiophene, Polyglycolic acid fibre, Polyglycolic acid fibre and polystyrolsulfon acid compound one or more.
8. quinone-manganese oxide lithium water system the battery filled according to claim 1, it is characterized in that: described cell shapes is takeup type cylinder type, laminated type square or coin shape, the shell of described battery is organic plastics, metal material or metal organic composite material.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011504A (en) * | 2017-05-06 | 2017-08-04 | 中国科学院青岛生物能源与过程研究所 | One class is rich in the two-dimentional carbon-rich material preparation method and applications of carbonyl, thioketones and selenone functional group |
| CN107482242A (en) * | 2017-07-16 | 2017-12-15 | 常州大学 | A kind of water system single flow battery based on metal organic complex liquid stream positive pole and preparation method thereof |
| CN109585881A (en) * | 2018-10-25 | 2019-04-05 | 中盐金坛盐化有限责任公司 | The organic flow battery system of the aqueous phase system with mixed solvent based on salt cave |
| CN110474111A (en) * | 2019-06-20 | 2019-11-19 | 宋君 | 3.5V aquo-lithium ion battery |
| CN111211360A (en) * | 2018-11-22 | 2020-05-29 | 浙江浙能中科储能科技有限公司 | Additive modified aqueous zinc ion colloidal electrolyte and preparation method thereof |
| CN111525133A (en) * | 2020-03-25 | 2020-08-11 | 眉山顺应动力电池材料有限公司 | Composite conductive agent, lithium ion positive electrode material prepared from composite conductive agent and lithium ion battery |
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| CN116190694A (en) * | 2022-09-07 | 2023-05-30 | 南京航空航天大学 | Calcium ion group thermoelectric conversion and energy storage system |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1889292A (en) * | 2006-07-20 | 2007-01-03 | 复旦大学 | Lithium ion battery with pyridyl quinone derivative as negative pole material |
| CN104752727A (en) * | 2013-12-31 | 2015-07-01 | 华为技术有限公司 | Quinone compound-graphene composite material and preparation method thereof as well as flexible lithium secondary battery |
| CN104779394A (en) * | 2015-04-17 | 2015-07-15 | 复旦大学 | Aqueous lithium (sodium) ion battery mixed negative material |
-
2015
- 2015-08-31 CN CN201510547177.8A patent/CN105047933A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1889292A (en) * | 2006-07-20 | 2007-01-03 | 复旦大学 | Lithium ion battery with pyridyl quinone derivative as negative pole material |
| CN104752727A (en) * | 2013-12-31 | 2015-07-01 | 华为技术有限公司 | Quinone compound-graphene composite material and preparation method thereof as well as flexible lithium secondary battery |
| CN104779394A (en) * | 2015-04-17 | 2015-07-15 | 复旦大学 | Aqueous lithium (sodium) ion battery mixed negative material |
Cited By (13)
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| CN107011504B (en) * | 2017-05-06 | 2019-09-10 | 中国科学院青岛生物能源与过程研究所 | Two-dimentional carbon-rich material preparation method and applications of the one kind rich in carbonyl, thioketones and selenone functional group |
| CN107482242A (en) * | 2017-07-16 | 2017-12-15 | 常州大学 | A kind of water system single flow battery based on metal organic complex liquid stream positive pole and preparation method thereof |
| CN107482242B (en) * | 2017-07-16 | 2019-11-12 | 常州大学 | A kind of water system single flow battery and preparation method thereof based on metal organic complex liquid stream anode |
| CN109585881A (en) * | 2018-10-25 | 2019-04-05 | 中盐金坛盐化有限责任公司 | The organic flow battery system of the aqueous phase system with mixed solvent based on salt cave |
| CN111211360A (en) * | 2018-11-22 | 2020-05-29 | 浙江浙能中科储能科技有限公司 | Additive modified aqueous zinc ion colloidal electrolyte and preparation method thereof |
| CN111211360B (en) * | 2018-11-22 | 2021-07-06 | 浙江浙能中科储能科技有限公司 | Additive modified aqueous zinc ion colloidal electrolyte and preparation method thereof |
| CN110474111A (en) * | 2019-06-20 | 2019-11-19 | 宋君 | 3.5V aquo-lithium ion battery |
| CN111525133A (en) * | 2020-03-25 | 2020-08-11 | 眉山顺应动力电池材料有限公司 | Composite conductive agent, lithium ion positive electrode material prepared from composite conductive agent and lithium ion battery |
| CN115020660A (en) * | 2022-04-18 | 2022-09-06 | 湖北大学 | PQ-MnO 2 Composite electrode material and preparation method and application thereof |
| CN115020660B (en) * | 2022-04-18 | 2023-11-24 | 湖北大学 | PQ-MnO 2 Composite electrode material, preparation method and application thereof |
| CN116190694A (en) * | 2022-09-07 | 2023-05-30 | 南京航空航天大学 | Calcium ion group thermoelectric conversion and energy storage system |
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