CN101262056A - A water solution chargeable lithium ion battery - Google Patents
A water solution chargeable lithium ion battery Download PDFInfo
- Publication number
- CN101262056A CN101262056A CNA2007100379060A CN200710037906A CN101262056A CN 101262056 A CN101262056 A CN 101262056A CN A2007100379060 A CNA2007100379060 A CN A2007100379060A CN 200710037906 A CN200710037906 A CN 200710037906A CN 101262056 A CN101262056 A CN 101262056A
- Authority
- CN
- China
- Prior art keywords
- lithium
- ion battery
- electrolyte
- lithium ion
- water solution
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a water solution rechargeable lithium ion battery. The anode of the water solution rechargeable lithium ion battery adopts a manganese oxide compound of spinel type or metal or non metal material, and a cathode thereof adopts lithium vanadium oxide or doped material of metal or non metal; the electrolyte adopts a water solution containing lithium compound. The water solution rechargeable lithium ion battery of the invention has wide raw material sources, easy preparation, low cost, no environment pollution and long cycle life, solves the safety problem of the existing organic electrolyte lithium ion battery, has higher energy density and power density, can serve as power supply for various electrical appliances, and is especially suitable for being used as power cells for electric vehicles.
Description
Technical field
The invention belongs to battery and capacitor technology field, be specifically related to a kind of novel water solution chargeable lithium ion battery.
Background technology
Chemical power source is the device that chemical energy is converted into electric energy.Along with the development of society and the raising of people's lives, the purposes of chemical power source more and more widely, the importance in various electronic equipments, health care, communications and transportation and national defense construction is also increasing.The common chemical power supply is battery, secondary cell and fuel cell once, as zinc-manganese primary cell, lead-acid battery, Ni-MH battery, nickel-cadmium cell, lithium ion battery, hydrogen oxygen fuel cell etc.The some of them battery is to adopt the aqueous solution to do electrolyte, and some battery is to make electrolyte with organic liquid.The security performance of water system battery is good, and the conductivity of the aqueous solution is bigger than non-aqueous solution, can two-forty discharge and recharge, and in addition, water does not pollute environment.Organic electrolyte has wide electrochemical window, can obtain high-tension cell, thereby improves the specific energy of battery.The commercialization lithium ion battery adopts organic electrolyte exactly at present, and its embedding compound anodal and negative pole employing lithium ion is typically and uses LiCoO
2As positive pole, use material with carbon element as negative pole.In the time of charging, lithium ion is deviate from from positive pole, by electrolyte, embeds in the negative material; In the time of discharge, process is just in time opposite.This battery has high monomer voltage and high specific energy, is widely used in now in the portable electronic equipment, in mobile phone, notebook computer and digital camera.But this cell preparation process more complicated, assemble needs water-less environment, and the cost height owing to adopt organic electrolyte, in use exists potential safety hazard simultaneously.In order to solve the shortcoming of lithium ion battery, Canadian Moli Energy company has proposed water system chargeable battery (international patent WO 95/21470), its principle is identical with lithium ion battery, 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 its poor-performing, specific capacity is little, and especially the cycle performance of battery is poor, can not practical application.
Summary of the invention
The water solution chargeable lithium ion battery that the objective of the invention is to propose a kind ofly to have extended cycle life, power is big, cost is low, capacity is high.
The present inventor passes through research extensively and profoundly, found that to adopt Li
1+aV
3O
8(0≤a≤1) series compound is as negative pole, Li
1+xMn
2O
4(0≤x≤1) series compound is as positive pole, as electrolyte, can form a kind of novel high-performance water solution chargeable lithium ion battery with the aqueous solution of lithium-containing compound.This water solution chargeable lithium battery, it has extended cycle life, power is big, cost is low, capacity is high, and environmentally friendly.Have purposes widely, can be used 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.
Water solution chargeable lithium ion battery provided by the invention, the similar of the structure of this battery and existing organic system lithium ion battery is mainly formed by positive pole, negative pole, barrier film with as the aqueous solution of electrolytical lithium-containing compound.
Active material anodal described in the present invention is the dopant material of spinel lithium manganese oxide compound or its metal or nonmetalloid, and its composition can be expressed as Li
1+xMn
2-yM
yO
4-zN
z(0≤x≤1,0≤y≤1,0≤z≤1).Wherein M represents a kind of metallic element or the multiple metallic element that mixes, a kind of nonmetalloid or multiple nonmetalloid that the N representative is mixed.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 electrode.Above-mentioned material mixes the slurry that can make certain viscosity.This slurry is coated on the collector of electrode, obtains cathode film.The consumption proportion of each component is by weight: active material: electronic conductive material material: binding agent=80-90: 10-15: 5-10.
The active material of negative pole described in the present invention adopts the dopant material of lithium-barium oxide or its metal or nonmetalloid.Its composition can be expressed as Li
1+aMbV
3-bO
8-cN
c(0≤a≤1,0≤b≤1,0≤c≤1), wherein M represents a kind of metallic element or the multiple metallic element that mixes, a kind of nonmetalloid or multiple nonmetalloid that the N representative is mixed.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, make slurry, be coated on the collector of electrode, obtain the negative electrode film.Each amounts of components proportioning is by weight: active material: electronic conductive material: binding agent=80-90: 10-15: 5-10.
Electrolyte described in the present invention is the aqueous solution of lithium-containing compound.Wherein, lithium-containing compound is a kind of of lithium sulfate, lithium halide, lithium nitrate, lithium hydroxide, lithium phosphate, lithium acetate, lithium oxalate, or wherein several mixture.For improving the migration velocity of ionic conductivity and ion, can also add an amount of supporting electrolyte, as sulfate, nitrate, phosphate, acetate, oxalates, chloride, the mixed aqueous solution of one or more in fluoride or the hydroxide.Its cation comprises the mixture of one or more ions in alkali metal, alkaline-earth metal, rare earth metal, aluminium, magnesium or the zinc.The concentration of electrolyte solution is 0.1mol/l-15mol/l.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.
The positive electrode that is adopted among the present invention is a manganese sub-group compound, and negative material is a vanadium sub-group compound, the wide material sources of material, and preparation is easily, and is with low cost.
Water solution chargeable lithium battery provided by the invention has overcome the shortcoming of existing lithium ion battery, safe in utilization, power is big, have extended cycle life, cost is low, non-environmental-pollution, solved the safety issue of present organic electrolyte lithium ion battery, specific capacity and specific energy are than higher, be a kind of energy of green, can act on the power supply of various electrical equipment.Be particularly suitable as the electrical source of power of electric automobile.And technological process simplifies greatly, do not need harsh preparation conditions such as anhydrous and oxygen-free.
Description of drawings
Fig. 1 is the embodiment of the invention 1 LiV
3O
8//LiMn
2O
4The charging and discharging curve figure of battery.
Fig. 2 is the embodiment of the invention 2 Li
1.2V
3O
8//Li
1.1Mn
2O
4The 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
The LiMn that positive electrode adopts commercial Li-ion batteries to use
2O
4The positive plate composition is pressed LiMn
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 synthetic LiV
3O
8, cathode size is formed proportioning according to LiV
3O
8: conductive agent: binding agent=mix at 85: 10: 5, evenly coat then on the nickel screen collector, 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
4The aqueous solution is assembled into battery as electrolyte.The capacity of battery is 200mAh, and with the rate charge-discharge of 0.2C, charging and discharging curve circulates not have obviously for 300 times and decays as shown in Figure 1.
Positive electrode adopts synthetic Li
1.1Mn
2O
4The positive plate composition is pressed Li
1.1Mn
2O
4: 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 synthetic Li
1.2V
3O
8, cathode size is formed proportioning according to Li
1.2V
3O
8: conductive agent: binding agent=mix at 80: 15: 5, evenly coat then on the nickel screen collector, be pressed into electrode after the oven dry.The nonwoven fabrics that employing commercial alkaline manganese cell is used is used 8MLiNO as barrier film
3Solution is assembled into battery as electrolyte.The capacity of battery is 150.3mAh, and with the rate charge-discharge of 1C, charging and discharging curve circulates not have obviously for 400 times and decays as shown in Figure 2.
Embodiment 3
Positive electrode adopts synthetic LiCr
0.012Mn
1.998O
4The positive plate composition is pressed LiCr
0.012Mn
1.998O
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 Li
1.25V
2.95O
7.8F
0.2, cathode size is formed proportioning according to Li
1.25V
2.95O
7.8F
0.2: conductive agent: binding agent=mix at 80: 10: 10, evenly coat then on the nickel screen collector, 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
4The aqueous solution is assembled into battery as electrolyte.The capacity of battery is 195mAh, and with the rate charge-discharge of 0.2C, circulating does not have obviously decay for 400 times.
Positive electrode adopts synthetic LiMn
1.9Co
0.1O
4The positive plate composition is pressed LiMn
1.9Co
0.1O
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 Li
1.2V
2.8925Ti
0.1075O
7.9F
0.1, cathode size is formed proportioning according to Li
1.2V
2.8925Ti
0.1075O
7.9F
0.1: conductive agent: binding agent=mix at 80: 10: 10, evenly coat then on the nickel screen collector, be pressed into electrode after the oven dry.The nonwoven fabrics that employing commercial alkaline manganese cell is used is used 4M Li as barrier film
2SO
4The aqueous solution is assembled into battery as electrolyte.The capacity of battery is 180mAh, and with the rate charge-discharge of 1C, circulating does not have obviously decay for 300 times.
Embodiment 5
Positive electrode adopts synthetic Li
1.02Co
0.1Ni
0.1Mn
1.8O
4The positive plate composition is pressed Li
1.02Co
0.1Ni
0.1Mn
1.8O
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 Li
1.2V
2.8Ti
0.1Mo
0.1O
7.9F
0.1, cathode size is formed proportioning according to Li
1.2V
2.8Ti
0.1Mo
0.1O
7.9F
0.1: conductive agent: binding agent=mix at 80: 10: 10, evenly coat then on the nickel screen collector, be pressed into electrode after the oven dry.The nonwoven fabrics that employing commercial alkaline manganese cell is used as electrolyte, is assembled into battery with the 10M LiCl aqueous solution as barrier film.The capacity of battery is 180mAh, and with the rate charge-discharge of 1C, circulating does not have obviously decay for 400 times.
Embodiment 6
Positive electrode adopts synthetic Li
1.1Mn
2O
3.95F
0.05The positive plate composition is pressed Li
1.1Mn
2O
3.95F
0.05: 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 synthetic Li
1.2V
3O
8, cathode size is formed proportioning according to Li
1.2V
3O
8: conductive agent: binding agent=mix at 85: 10: 5, evenly coat then on the nickel screen collector, 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
4The aqueous solution is assembled into battery as electrolyte.The capacity of battery is 200mAh, and with the rate charge-discharge of 0.5C, circulating does not have obviously decay for 500 times.
Claims (3)
1. a water solution chargeable lithium ion battery is made up of positive pole, negative pole, barrier film and electrolyte, it is characterized in that the anodal dopant material that adopts spinel lithium manganese oxide compound or its metal or nonmetalloid, and its composition is expressed as Li
1+xMn
2-yM
yO
4-zN
z, 0≤x≤1,0≤y≤1,0≤z≤1, wherein M represents a kind of metallic element or the multiple metallic element that mixes, a kind of nonmetalloid or multiple nonmetalloid that the N representative is mixed; Negative pole adopts the dopant material of lithium-barium oxide or its metal or nonmetalloid, and its composition is expressed as Li
1+aM
bV
3-bO
8-cN
c, 0≤a≤1,0≤b≤1,0≤c≤1, wherein M represents a kind of metallic element or the multiple metallic element that mixes, a kind of nonmetalloid or multiple nonmetalloid that the N representative is mixed; Electrolyte is the aqueous solution of lithium-containing compound.
2. water solution chargeable lithium ion battery according to claim 1, it is characterized in that lithium-containing compound in the described electrolyte is one or more mixtures in lithium sulfate, lithium halide, lithium nitrate, lithium hydroxide, lithium phosphate, lithium acetate or the lithium oxalate, electrolytical concentration is 0.1mol/1-15mol/l.
3. water solution chargeable lithium ion battery according to claim 1, it is characterized in that adding in the described electrolyte supporting electrolyte is arranged, described supporting electrolyte is sulfate, nitrate, phosphate, acetate, oxalates, chloride, the mixture of one or more in fluoride or the hydroxide; Cation in the electrolyte is the mixture of one or more ions in alkali metal, alkaline-earth metal, rare earth metal, aluminium, magnesium or the zinc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100379060A CN101262056A (en) | 2007-03-08 | 2007-03-08 | A water solution chargeable lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100379060A CN101262056A (en) | 2007-03-08 | 2007-03-08 | A water solution chargeable lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101262056A true CN101262056A (en) | 2008-09-10 |
Family
ID=39962356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100379060A Pending CN101262056A (en) | 2007-03-08 | 2007-03-08 | A water solution chargeable lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101262056A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102110839A (en) * | 2009-12-29 | 2011-06-29 | 万向电动汽车有限公司 | Battery |
| CN101656329B (en) * | 2009-09-22 | 2011-08-31 | 西安交通大学 | Preparation method of inorganic aqueous solution lithium ion battery |
| CN102438948A (en) * | 2009-05-27 | 2012-05-02 | 科诺科菲利浦公司 | Methods of making lithium vanadium oxide powders and uses of the powders |
| CN101728525B (en) * | 2008-10-30 | 2012-06-06 | 比亚迪股份有限公司 | Cathode active substance of lithium secondary battery and preparation method thereof |
| CN102496746A (en) * | 2011-12-23 | 2012-06-13 | 常州大学 | Water-soluble lithium ion battery |
| WO2013155964A1 (en) * | 2012-04-17 | 2013-10-24 | 苏州宝时得电动工具有限公司 | Battery |
| CN103500821A (en) * | 2013-10-18 | 2014-01-08 | 厦门大学 | Low potential lithium-vanadium-based compound for lithium ion batteries and preparation method thereof |
| CN103531744A (en) * | 2012-07-05 | 2014-01-22 | 苏州宝时得电动工具有限公司 | Battery plate and electrode manufacturing method |
| CN104321276A (en) * | 2012-07-06 | 2015-01-28 | 松下知识产权经营株式会社 | Carbon-based material, electrode catalyst, electrode, gas diffusion electrode, electrochemical device, fuel battery, and process for producing carbon-based material |
| CN111525123A (en) * | 2020-04-29 | 2020-08-11 | 国家纳米科学中心 | Cathode material of water-based lithium ion battery and preparation method and application thereof |
-
2007
- 2007-03-08 CN CNA2007100379060A patent/CN101262056A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101728525B (en) * | 2008-10-30 | 2012-06-06 | 比亚迪股份有限公司 | Cathode active substance of lithium secondary battery and preparation method thereof |
| CN102438948A (en) * | 2009-05-27 | 2012-05-02 | 科诺科菲利浦公司 | Methods of making lithium vanadium oxide powders and uses of the powders |
| CN101656329B (en) * | 2009-09-22 | 2011-08-31 | 西安交通大学 | Preparation method of inorganic aqueous solution lithium ion battery |
| CN102110839A (en) * | 2009-12-29 | 2011-06-29 | 万向电动汽车有限公司 | Battery |
| WO2011079482A1 (en) * | 2009-12-29 | 2011-07-07 | 万向电动汽车有限公司 | Battery |
| CN102496746A (en) * | 2011-12-23 | 2012-06-13 | 常州大学 | Water-soluble lithium ion battery |
| CN102496746B (en) * | 2011-12-23 | 2014-08-13 | 常州大学 | Water-soluble lithium ion battery |
| WO2013155964A1 (en) * | 2012-04-17 | 2013-10-24 | 苏州宝时得电动工具有限公司 | Battery |
| CN103427119A (en) * | 2012-04-17 | 2013-12-04 | 苏州宝时得电动工具有限公司 | Battery with a battery cell |
| CN103427119B (en) * | 2012-04-17 | 2016-05-18 | 苏州宝时得电动工具有限公司 | Battery with a battery cell |
| CN103531744A (en) * | 2012-07-05 | 2014-01-22 | 苏州宝时得电动工具有限公司 | Battery plate and electrode manufacturing method |
| CN104321276A (en) * | 2012-07-06 | 2015-01-28 | 松下知识产权经营株式会社 | Carbon-based material, electrode catalyst, electrode, gas diffusion electrode, electrochemical device, fuel battery, and process for producing carbon-based material |
| CN104321276B (en) * | 2012-07-06 | 2016-07-06 | 松下知识产权经营株式会社 | The preparation method of carbon-based material, electrode catalyst, electrode, gas-diffusion electrode, electrochemical appliance, fuel cell and carbon-based material |
| CN103500821A (en) * | 2013-10-18 | 2014-01-08 | 厦门大学 | Low potential lithium-vanadium-based compound for lithium ion batteries and preparation method thereof |
| CN103500821B (en) * | 2013-10-18 | 2016-04-13 | 苏州德尔石墨烯产业投资基金管理有限公司 | A kind of lithium ion battery electronegative potential lithium vanadium based compound and preparation method thereof |
| CN111525123A (en) * | 2020-04-29 | 2020-08-11 | 国家纳米科学中心 | Cathode material of water-based lithium ion battery and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1328818C (en) | Mixed aquo-lithium ion battery | |
| CN103700820B (en) | A kind of lithium ion selenium battery with long service life | |
| CN101262056A (en) | A water solution chargeable lithium ion battery | |
| CN101087018A (en) | A water solution Na ion chargeable battery | |
| CN104779394A (en) | Aqueous lithium (sodium) ion battery mixed negative material | |
| CN103972497B (en) | Lithium ion battery Co2snO4/ C nano composite negative pole material and preparation and application thereof | |
| CN103022577A (en) | Water system chargeable sodium-ion battery | |
| CN101221853A (en) | Semi-solid state or full-solid state water system super capacitor | |
| CN102738442A (en) | High energy density charge-discharge lithium battery | |
| CN102969473A (en) | Organic/inorganic composite porous thin film and electrochemical energy storing device using same | |
| CN102082259A (en) | Lithium secondary battery electrodes and production method thereof | |
| CN103855389A (en) | Ferric (III) fluoride / carbon composite material and its preparation method and application | |
| CN103066281A (en) | Synergistically modified lithium-iron-phosphate positive active material enveloped with graphene three-dimensional network and doped with metal ions and preparation method of lithium-iron-phosphate positive active material | |
| CN104795567B (en) | Aquo-lithium ion/sodium-ion battery based on iodide ion solution anode and organic matter cathode | |
| CN104795564B (en) | A kind of positive electrode of Aqueous solution secondary battery, pole piece, secondary cell and purposes | |
| CN104134818A (en) | High-energy-density lithium ion battery and preparation method thereof | |
| CN104795555A (en) | Aqueous-solution sodium-ion battery and cathode material, preparation method and application thereof | |
| CN102916195A (en) | Graphene-coated copper oxide composite cathode material and method for manufacturing same | |
| CN105789553A (en) | Positive electrode of lithium ion battery | |
| CN102157753A (en) | Fast-charging high-power winding column type lithium ion battery | |
| CN105047916A (en) | Method for improving electrochemical properties of lithium iron phosphate with copper/graphene | |
| CN106410194A (en) | Composite lithium battery and preparation method thereof | |
| CN102263280A (en) | Flow aqueous chargeable alkali metal ion battery | |
| CN101409344A (en) | Lithium ion battery cathode material and preparation method thereof | |
| CN108461712A (en) | A kind of potassium/potassium ferrite/Prussian blue solid state battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20080910 |