CN101262076A - A water solution chargeable lithium battery - Google Patents
A water solution chargeable lithium battery Download PDFInfo
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- CN101262076A CN101262076A CNA200710037908XA CN200710037908A CN101262076A CN 101262076 A CN101262076 A CN 101262076A CN A200710037908X A CNA200710037908X A CN A200710037908XA CN 200710037908 A CN200710037908 A CN 200710037908A CN 101262076 A CN101262076 A CN 101262076A
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- water solution
- lithium battery
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- chargeable lithium
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- 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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a novel water solution chargeable lithium battery with high performance. A substance, which is capable of inserting and off-inserting lithium-ion, is adopted as the anode of the water-solution chargeable lithium battery; materials like high molecular polymers, which are capable of doping or off-doping other matters, are adopted as the cathode; water solution containing lithium-ion is adopted as the electrolyte. The novel water solution chargeable lithium battery of the invention, by organically combination of inserting and off-inserting mechanism of lithium and doping and off-doping mechanism of high molecular polymer into one energy storing system, has the advantages of low cost, no environment pollution and long service life, solves safety problem of the existing lithium-ion battery, has comparatively high energy density and power density, integrates the advantages of a lithium-ion battery and a capacitor and can be used as power of various electrical appliances.
Description
Technical field
The invention belongs to the battery technology field, be specifically related to a kind of novel water solution chargeable lithium battery (AqueousRechargeable Lithium Battery:ARLB can be called for short " water lithium ").
Background technology
As everyone knows, along with the economy in the whole world develops rapidly and being on the increase of population, energy shortage and problem of environmental pollution are serious day by day.The theory of taking into account the sustainable development of economic growth, energy resource supply and environmental protection has become the theme in the world.Conversion of energy and the storage system of exploring new green have become very urgent subject.In addition, the electric vehicle engineering as effective alleviation energy shortage and problem of environmental pollution is subject to people's attention day by day.The implementation of electric automobile and the universal pressure that not only can alleviate national Imported oil, and the pollution that can alleviate vehicle exhaust significantly.Countries in the world are all at the active development electric automobile and obtain certain progress, yet the bottleneck of electric vehicle engineering is its electrical source of power.Electrical source of power as electric automobile mainly contains rechargeable battery, fuel cell and electrochemical capacitor at present.Wherein rechargeable battery mainly is lead acid accumulator, Ni-MH battery and lithium ion battery.But take all factors into consideration its cost, fail safe, distance travelled, acceleration capacity and, still do not have a kind of power supply can satisfy the requirement of electric automobile at present the influence of environment.The lead acid accumulator specific energy is low, and plumbous poisonous; Ni-MH battery is too expensive, and specific capacity is little; The lithium ion battery high rate during charging-discharging is poor, has safety problem simultaneously.Though having, electrochemical capacitor has extended cycle life, high power output, and energy density is too little, and fuel cell cost height and power output are little, can not satisfy the requirement of startup, acceleration and the climbing of electric motor car.For solving the shortcoming of existing battery, people update the technology and the new battery of exploitation of existing battery.Canadian Moli Energy company has proposed aquo-lithium ion lithium battery (international patent WO95/21470), and its principle is identical with the lithium ion battery of existing organic system, and the both positive and negative polarity of regulation battery all adopts lithium ion to embed compound, as LiCoO
2, LiMn
2O
4, VO
2Deng.But the cycle performance of its poor-performing, especially battery.The someone found that mixed aquo-lithium ion battery had good fast charging and discharging performance (Y.G.Wang afterwards, etal., Electrochem.Commun., 2005,7:1138-1142), its negative pole is used activated carbon instead, and the anodal lithium ion that adopts embeds compound, its principle is that lithium ion embedding in positive pole is taken off and the absorption on negative electrode active carbon, is the mixed type system of a kind of lithium ion battery and traditional capacitor.Its cycle performance is good, but its specific capacity is less, and has bigger self discharge problem.
Summary of the invention
The purpose of this invention is to provide a kind ofly have extended cycle life, power is big, cost is low, capacity is high water solution chargeable lithium battery,
The present inventor passes through research extensively and profoundly, found that and adopt lithium ion to mix and the macromolecular material of dedoping is that negative pole, the lithium ion material that reversible embedding can take place and take off embedding is as positive pole, as electrolyte, can form a kind of novel high-performance water solution chargeable lithium battery with the aqueous solution of lithium-containing compound.The having extended cycle life of the water solution chargeable lithium battery that this is novel, power is big, cost is low, capacity is high, and environmentally friendly, has purposes widely, as large-scale energy-storage system; Be used for various portable electronic equipments and housed device; Be used as the power supply of various power set etc.
Water solution chargeable lithium battery provided by the invention, the similar of its structure and existing organic system lithium ion battery is made up of positive pole, negative pole, barrier film and the aqueous solution with ionic conductivity.
Active material anodal described in the present invention is that lithium ion can embed and take off the material of embedding; Specifically can be the compounds such as oxide, sulfide, phosphide, chloride, phosphate or sulfate of transition metal.LiMn for example
2O
4, LiCoO
2, LiNiO
2, LiCo
1/3Ni
1/3Mn
1/3O
2, LiMnO
2, LiFePO
4, V
2O
5Deng, and other metal or nonmetal doping material beyond the containing metal in these compounds.Can also add an amount of electronic conductive material (as material of graphite, carbon black, acetylene black, metal dust or other conduction etc.) and binding agent (as PVDF, polytetrafluoroethylene, cellulose, water-soluble rubber etc.) in the positive pole.Its consumption is by weight: active material: electronic conductive material: binding agent=80-90: 5-10: 5-10.
The active material of negative pole described in the present invention is that lithium ion can mix and the macromolecular material of dedoping, or the composite material of this macromolecular material and inorganic or organic compound.Polymer such as polyacetylene, polyaniline, polypyrrole, polythiophene, poly-phenylene vinylene (ppv) for example, or the copolymer of the monomer derived thing of these polymer, or the copolymer of several monomers, or in conducting polymer, add the mixture of inorganic compound or organic compound, concrete as LiMn
2O
4, LiV
3O
8, VO
2, RuO
2, active carbon, other polymer etc.In order to improve the electron conduction of electrode, also can add an amount of above-mentioned electronic conductive material, mix with above-mentioned binding agent again, its consumption is by weight: active material: electronic conductive material: binding agent=80-90: 5-10: 5-10.
Electrolyte described in the present invention has the lithium ion conducting ability, is one or more the mixed aqueous solution in sulfate, nitrate, phosphate, acetate, chloride, fluoride or the hydroxide.Its cation is lithium ion, for example Li
2SO
4, LiCl, LiNO
3, LiOH, Li
3PO
4Deng solution.For improving the migration velocity of ionic conductivity and ion, can also add an amount of supporting electrolyte, as KCl, K
2SO
4, NaCl, Na
2SO
4Deng.Can also add an amount of filler in the electrolyte, for example inorganic the or organic substance of molecular sieve, porous is made gelatinous electrolyte.
Barrier film described in the present invention can adopt organic material or inorganic material barrier film, work out barrier film, felted film, paper barrier film, ceramic diaphragm etc., as glass fibre, nylon cloth, polypropylene mat, vinylon, nonwoven fabrics etc.
The basic functional principle of water solution chargeable lithium battery provided by the invention is: in the charging process, lithium ion is deviate from from positive pole, and in polymer the reaction (doping) of mixing takes place; In the discharge process, polymer generation dedoping reaction (undoping), lithium ion embeds in the positive electrode.
The negative material that is adopted among the present invention is that lithium ion can mix and the macromolecular material of dedoping, the wide material sources of material, and preparation is easily, conduct electricity very well, be processed into film easily, the reversibility of doping and dedoping is good, has very long cycle life.The novel water solution chargeable lithium battery of this kind is safe in utilization, power big, have extended cycle life, cost is low, has thoroughly solved the safety problem of existing lithium ion battery.Specific capacity and specific energy than traditional capacitor improve greatly, non-environmental-pollution, be a kind of energy of green.
Water solution chargeable lithium battery provided by the invention has overcome the shortcoming separately of battery and capacitor, combines the advantage of battery and capacitor, and technological process simplifies greatly, does not need harsh preparation conditions such as anhydrous and oxygen-free.
Energy-storage system involved in the present invention has purposes widely, can be used for various electrical appliances such as electronic chip, wireless headset, wrist-watch, mobile phone, computer, camera, video camera, MP3, electronic toy, electric bicycle, battery-operated motor cycle, electric automobile.
Description of drawings
Fig. 1 embodiment of the invention 1 polyaniline //LiMn
2O
4The charging and discharging curve figure of battery.
Fig. 2 embodiment of the invention 2 polypyrroles //LiCoO
2The discharge of battery, charge graph.
Embodiment
To be described in more detail the present invention by specific embodiment below, but protection scope of the present invention is not limited to these embodiment.
Embodiment 1
Positive electrode adopts the used LiMn of commercial Li-ion batteries
2O
4Press LiMn anodal the composition
2O
4: carbon black: the part by weight of binding agent=80: 10: 10 mixes, and coats on the nickel screen collector, is pressed into electrode after the oven dry.Negative material adopts polyaniline, and cathode size is formed proportioning according to polyaniline: conductive agent: binding agent=mix at 80: 10: 10, evenly coat then on the nickel screen collector, and be pressed into electrode after the oven dry.The nonwoven fabrics that employing commercial alkaline manganese cell is used is used 2M Li as barrier film
2SO
4Solution is assembled into battery as electrolyte.The capacity of battery is 200mAh, and with the rate charge-discharge of 0.3C, charging and discharging curve circulates not have obviously for 1000 times and decays as shown in Figure 1.
Embodiment 2
Positive electrode adopts the used LiCoO of commercial Li-ion batteries
2Press LiCoO anodal the composition
2: carbon black: the part by weight of binding agent=80: 15: 5 mixes, and coats on the nickel screen collector, is pressed into electrode after the oven dry.Negative material adopts polypyrrole, and cathode size is formed proportioning according to polypyrrole: conductive agent: binding agent=mix at 85: 10: 5, evenly coat then on the nickel screen collector, and be pressed into electrode after the oven dry.The nonwoven fabrics that employing commercial alkaline manganese cell is used is used 1M Li as barrier film
2SO
4Solution is assembled into battery as electrolyte.The capacity of battery is 240mAh, and with the rate charge-discharge of 0.5C, charging and discharging curve circulates not have obviously for 500 times and decays as shown in Figure 2.
Embodiment 3
Positive electrode adopts the used LiMn of commercial Li-ion batteries
2O
4Press LiMn anodal the composition
2O
4: carbon black: the part by weight of binding agent=85: 10: 5 mixes, and coats on the nickel screen collector, is pressed into electrode after the oven dry.Negative material adopts polypyrrole, and cathode size is formed proportioning according to polypyrrole: conductive agent: binding agent=mix at 80: 10: 10, evenly coat then on the nickel screen collector, and be pressed into electrode after the oven dry.The nonwoven fabrics that the employing alkaline Mn cell is used is used 2M Li as barrier film
2SO
4Solution is assembled into battery as electrolyte.The specific capacity of battery is 210mAh, and with the rate charge-discharge of 1C, 500 capacity that circulate do not have obvious decay.
Embodiment 4
Positive electrode adopts the used LiCoO of commercial Li-ion batteries
2Press LiCoO anodal the composition
2: carbon black: the part by weight of binding agent=80: 10: 10 mixes, and coats on the nickel screen collector, is pressed into electrode after the oven dry.Negative material adopts polyaniline, and cathode size is formed proportioning according to polyaniline: conductive agent: binding agent=mix at 80: 10: 10, evenly coat then on the nickel screen collector, and be pressed into electrode after the oven dry.The nonwoven fabrics that the employing alkaline Mn cell is used is used 2M Li as barrier film
2SO
4Solution is assembled into battery as electrolyte.The specific capacity of battery (calculating with positive electrode) is 135mAh, and with the rate charge-discharge of 1C, circulating does not have obviously decay for 1000 times.
Embodiment 5
Positive electrode adopts the used LiCo of commercial Li-ion batteries
1/3Ni
1/3Mn
1/3O
2Press LiCo anodal the composition
1/3Ni
1/3Mn
1/3O
2: carbon black: the part by weight of binding agent=80: 10: 10 mixes, and coats on the nickel screen collector, is pressed into electrode after the oven dry.Negative material adopts commercial polyaniline, and cathode size is formed proportioning according to polyaniline: conductive agent: binding agent=mix at 80: 10: 10, evenly coat then on the nickel screen collector, and be pressed into electrode after the oven dry.The nonwoven fabrics that employing commercial alkaline manganese cell is used is used 2M Li as barrier film
2SO
4Solution is assembled into battery as electrolyte.The capacity of battery is 195mAh, and with the rate charge-discharge of 0.5C, circulating does not have obviously decay for 1000 times.
Embodiment 6
Positive electrode adopts the used LiMn of commercial Li-ion batteries
2O
4Press LiMn anodal the composition
2O
4: carbon black: the part by weight of binding agent=80: 10: 10 mixes, and coats on the nickel screen collector, is pressed into electrode after the oven dry.Negative material adopts synthetic polythiophene, and cathode size is formed proportioning according to polythiophene: conductive agent: binding agent=mix at 85: 5: 10, evenly coat then on the nickel screen collector, and be pressed into electrode after the oven dry.Adopt the used barrier film of alkaline Mn cell, use 2M Li
2SO
4Solution is assembled into battery as electrolyte.The specific capacity of battery is 120mAh, and with the rate charge-discharge of 1C, circulating does not have obviously decay for 1000 times.
Claims (7)
1. water solution chargeable lithium battery, form by positive pole, negative pole, barrier film and electrolyte, it is characterized in that the anodal lithium ion that adopts can embed and take off the material of embedding, negative pole adopts lithium ion to mix and the macromolecular material of dedoping, or the composite material of this macromolecular material and inorganic or organic compound, electrolyte adopts the aqueous solution with ionic conductivity.
2. water solution chargeable lithium battery according to claim 1 is characterized in that described anodal oxide, sulfide, phosphide, chloride, phosphate or the sulfate that adopts transition metal.
3. water solution chargeable lithium battery according to claim 1 is characterized in that described negative pole adopts polyacetylene, polyaniline, polypyrrole, polythiophene or poly-phenylene vinylene (ppv), or the copolymer of the polymer of monomer whose derivative or several monomers.
4. water solution chargeable lithium battery according to claim 1, it is characterized in that described electrolyte is one or more the mixed aqueous solution in sulfate, nitrate, phosphate, acetate, chloride, fluoride or the hydroxide, its cation is a lithium ion.
5. water solution chargeable lithium battery according to claim 1 is characterized in that the material that described lithium ion could embed and take off embedding is LiMn
2O
4, LiCoO
2, LiNiO
2, LiCo
1/3Ni
1/3Mn
1/3O
2, LiMnO
2, LiFePO
4Or V
2O
5, or other metal of these compounds or the dopant material of nonmetalloid.
6. water solution chargeable lithium battery according to claim 1 is characterized in that described electrolyte can add an amount of supporting electrolyte.
7. water solution chargeable lithium battery according to claim 1 is characterized in that described negative pole adopts LiMn
2O
4, LiV
3O
8, VO
2, R
uO
2Or active carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200710037908XA CN101262076A (en) | 2007-03-08 | 2007-03-08 | A water solution chargeable lithium battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200710037908XA CN101262076A (en) | 2007-03-08 | 2007-03-08 | A water solution chargeable lithium battery |
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| Publication Number | Publication Date |
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| CN101262076A true CN101262076A (en) | 2008-09-10 |
Family
ID=39962373
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102610863A (en) * | 2012-03-19 | 2012-07-25 | 西安交通大学 | Method for assembling aqueous lithium-ion battery by aid of lithium iron manganese phosphate |
| CN104779394A (en) * | 2015-04-17 | 2015-07-15 | 复旦大学 | Aqueous lithium (sodium) ion battery mixed negative material |
| CN104795567A (en) * | 2015-04-17 | 2015-07-22 | 复旦大学 | Water system lithium-ion/sodium-ion battery based on iodide ion solution cathode and organic matter anode |
| CN106129363A (en) * | 2016-07-27 | 2016-11-16 | 芜湖凯尔电气科技有限公司 | Internet of Things long-life thin battery |
| CN106654273A (en) * | 2017-02-06 | 2017-05-10 | 安徽鹰龙工业设计有限公司 | Organic cathode material for lithium battery, and preparation method thereof |
| CN107082453A (en) * | 2017-03-24 | 2017-08-22 | 哈尔滨工程大学 | Preparation and application process as the hydrated iron barium oxide of water system Magnesium ion battery negative material |
| CN114861527A (en) * | 2022-04-15 | 2022-08-05 | 南京工业大学 | Lithium battery life prediction method based on time series characteristics |
| CN114937765A (en) * | 2022-05-27 | 2022-08-23 | 山东海科创新研究院有限公司 | Modified polyimide-coated silicon/lithium silicate negative electrode material, preparation method thereof and lithium ion battery |
-
2007
- 2007-03-08 CN CNA200710037908XA patent/CN101262076A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102610863A (en) * | 2012-03-19 | 2012-07-25 | 西安交通大学 | Method for assembling aqueous lithium-ion battery by aid of lithium iron manganese phosphate |
| CN104779394A (en) * | 2015-04-17 | 2015-07-15 | 复旦大学 | Aqueous lithium (sodium) ion battery mixed negative material |
| CN104795567A (en) * | 2015-04-17 | 2015-07-22 | 复旦大学 | Water system lithium-ion/sodium-ion battery based on iodide ion solution cathode and organic matter anode |
| CN104795567B (en) * | 2015-04-17 | 2018-06-26 | 复旦大学 | Aquo-lithium ion/sodium-ion battery based on iodide ion solution anode and organic matter cathode |
| CN106129363A (en) * | 2016-07-27 | 2016-11-16 | 芜湖凯尔电气科技有限公司 | Internet of Things long-life thin battery |
| CN106654273A (en) * | 2017-02-06 | 2017-05-10 | 安徽鹰龙工业设计有限公司 | Organic cathode material for lithium battery, and preparation method thereof |
| CN107082453A (en) * | 2017-03-24 | 2017-08-22 | 哈尔滨工程大学 | Preparation and application process as the hydrated iron barium oxide of water system Magnesium ion battery negative material |
| CN107082453B (en) * | 2017-03-24 | 2019-01-15 | 哈尔滨工程大学 | The preparation of hydrated iron barium oxide as water system Magnesium ion battery negative electrode material and application method |
| CN114861527A (en) * | 2022-04-15 | 2022-08-05 | 南京工业大学 | Lithium battery life prediction method based on time series characteristics |
| CN114937765A (en) * | 2022-05-27 | 2022-08-23 | 山东海科创新研究院有限公司 | Modified polyimide-coated silicon/lithium silicate negative electrode material, preparation method thereof and lithium ion battery |
| CN114937765B (en) * | 2022-05-27 | 2024-04-19 | 山东海科创新研究院有限公司 | Modified polyimide coated silicon/lithium silicate negative electrode material, preparation method thereof and lithium ion battery |
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Open date: 20080910 |