CN101087018A - A water solution Na ion chargeable battery - Google Patents

A water solution Na ion chargeable battery Download PDF

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Publication number
CN101087018A
CN101087018A CN 200710042919 CN200710042919A CN101087018A CN 101087018 A CN101087018 A CN 101087018A CN 200710042919 CN200710042919 CN 200710042919 CN 200710042919 A CN200710042919 A CN 200710042919A CN 101087018 A CN101087018 A CN 101087018A
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China
Prior art keywords
water solution
sodium
chargeable battery
battery
electrolyte
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CN 200710042919
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Chinese (zh)
Inventor
王高军
张汉平
赵娜红
吴宇平
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复旦大学
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Priority to CN 200710042919 priority Critical patent/CN101087018A/en
Publication of CN101087018A publication Critical patent/CN101087018A/en

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    • Y02E60/12

Abstract

The invention belongs to filed of battery and capacitor technique, specially a water solution natrium ion battery. The positive pole of the battery adopts material which the natrium ion can be embedded and unembeded and possesses high embedded/unembeded platform, negative pole of the material which the natrium ion can be embedded and unembeded and possesses low embedded/unembeded platform, the electrolyte adopts water solution which includes natrium compound. The water solution natrium ion battery in the invention, material is wide, easy to produce; cost is low, without pollution, circulate life is long, energy density and power density are high, it can be used to produce power source for various wirings, especially for drive battery of electric car.

Description

A kind of water solution Na ion chargeable battery

Technical field

The invention belongs to battery and capacitor technology field, be specifically related to a kind of novel water solution Na ion chargeable battery.

Background technology

Since Japanese Sony Corporation successfully released lithium ion battery, lithium ion battery had just obtained using widely in many-sides such as electronic product, military fields rapidly, to the development of auto industry aspect, became the electrokinetic cell of electric automobile first-selection at present.Remain the focus of various fields researchs such as current electrochemistry, material science and solid-state physics about the research of aspects such as the material of lithium ion battery, performance, application.But existing lithium ion battery all is to adopt organic electrolyte, thereby has inherent insecurity and lower high rate performance, needs strict control moisture in the production process, and in addition, the electrolyte that lithium ion battery is used and the price of lithium salts are also relatively more expensive.Recently, the Wu Yuping of Fudan University professor's seminar has developed a kind of water solution chargeable lithium battery (Aqueous rechargeable lithium battery:ARLB) and has overcome above shortcoming (referring to Gaojun Wang, Lijun Fu, Nahong Zhao, Lichun Yang, Yuping Wu, Haoqing Wu.Angew.Chem.Int.Ed, 2007,46:295-297).Because sodium and lithium are in same main group, and many similarities are arranged in nature, therefore, theoretically, sodium ion also can be used for constructing a kind of " rocking chair type " secondary cell.This has been that many scholars confirm.U.S. Willens Technologies, Inc. has applied for the sodium-ion battery and the corresponding positive and negative pole material (international patent WO02097907) of non-aqueous system.Because the cost of material of sodium-ion battery is lower than lithium ion battery, simultaneously, can adopt the lower electrolyte of decomposition voltage, therefore has certain advantage.Can be used for present electronic product as lithium ion battery, as products such as notebook computer, digital camera, mobile phones, can also be used for satellite, warship, submarine, aviation and military communication apparatus, market prospects are extensive.But, because the research of the aspects such as embedding mechanism of material, sodium ion is not still not deeply, so the industrialization of sodium-ion battery also takes day.In addition, the present sodium-ion battery of studying all is to adopt organic bath, and is poor at aspect of performances such as multiplying power dischargings.

In order to overcome the problem that above-mentioned sodium-ion battery exists, we are through research, exploration, find to adopt the aqueous solution as electrolyte, the embedding compound that contains sodium is as positive pole and negative material, can obtain a kind of new battery, i.e. water solution chargeable sode cell (Aqueous rechargeable sodium battery:ARSB) of discharging and recharging.

Summary of the invention

The objective of the invention is to the water solution Na ion chargeable battery that safe in utilization, power is big, have extended cycle life.

The water solution Na ion chargeable battery that the present invention proposes, the operation principle of its operation principle and existing lithium ion battery, sodium-ion battery and water solution chargeable lithium battery (ARLB) is similar.During charging, sodium ion is deviate from from positive pole, embeds in the negative pole by electrolyte then.During discharge, sodium ion is deviate from from negative pole, embeds in the positive pole by electrolyte, discharges electric energy simultaneously.

The water solution Na ion chargeable battery that the present invention proposes, the similar of its structure and existing organic system lithium ion battery mainly is made up of positive pole, negative pole, barrier film and the aqueous solution with ionic conductivity.

Anodal active material described in the present invention is that sodium ion can embed and takes off the relative high embedding of having of embedding/the take off material of current potential platform, as: the oxide of transition metal, sulfide, phosphide, chloride or compounds such as phosphate, sulfate.Preferred non-limiting example has NaMn 2O 4, NaCoO 2, NaNiO 2, NaCo 1/3Ni 1/3Mn 1/3O 2, NaMnO 2, NaFePO 4, NaV 2O 5Or NaVPO 4F etc., or other metal of its compound or nonmetal doping material.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 or water-soluble rubber etc.) in the positive pole.Above-mentioned material mixes the slurry that can make certain viscosity.This slurry is coated on the collector of electrode, obtains cathode film.

The active material of negative pole described in the present invention is that sodium ion can embed and takes off the relative low embedding of having of embedding/the take off material of current potential platform such as oxide, sulfide, phosphide, chloride or the compounds such as phosphate, sulfate of transition metal.Preferred non-limiting example has NaV 3O 8, VO 2, MnO 2, NaTiS 2, NaMoS 2, NaMoO 2Or NaWO 3Deng material, or other metal of its compound or nonmetal doping material.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 or water-soluble rubber etc.) in the negative pole.Above-mentioned material mixes the slurry that can make certain viscosity.This slurry is coated on the collector of electrode, obtains negative electrode film.

Electrolyte described in the present invention is the aqueous solution that contains sodium ion.For example solution such as sodium sulphate, sodium halide, sodium nitrate, NaOH, sodium phosphate, sodium acetate or sodium oxalate, or wherein several mixed solutions.For improving the migration velocity of ionic conductivity and ion, can also add an amount of supporting electrolyte, as sulfate, nitrate, phosphate, acetate, oxalates, or chloride, fluoride or hydroxide, or one or more mixed aqueous solution wherein.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.

Water solution chargeable sode cell provided by the invention has overcome the shortcoming of existing sodium-ion battery, safe in utilization, power is big, have extended cycle life, cost is low, non-environmental-pollution, and specific capacity and specific energy are higher, are a kind of energy of green, 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.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.

These purposes of the present invention and other purpose, feature and advantage will become clearer after reading whole specification in conjunction with the accompanying drawings.

Description of drawings

Fig. 1 is NaV in the embodiment of the invention 1 3O 8And NaMnO 2The XRD figure of material.

Fig. 2 is NaV in the embodiment of the invention 1 3O 8//NaMnO 2First three of battery time discharge curve.

Fig. 3 is NaV in the embodiment of the invention 2 3O 8//NaMnO 2Preceding ten charging and discharging curve figure of battery.

Embodiment

The present invention below will be described in more detail by specific embodiment, but protection scope of the present invention is not limited to these embodiment.

Embodiment 1

Positive electrode adopts the synthetic NaMnO of solid phase method 2(XRD analysis is seen accompanying drawing 1).The positive plate composition is pressed NaMnO 2: 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 NaV 3O 8(XRD analysis is seen accompanying drawing 1), cathode size are formed proportioning according to NaV 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 saturated Na as barrier film 2SO 4The aqueous solution is assembled into battery as electrolyte.The capacity of battery is 155mAh, with the rate charge-discharge of 0.1C, discharge curve as shown in Figure 2,300 capacity that circulate do not have obvious decay.

Embodiment 2

Positive electrode adopts synthetic NaMnO 2The positive plate composition is pressed NaMnO 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 NaV 3O 8, cathode size is formed proportioning according to NaV 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.Adopt nonwoven fabrics as barrier film, use 8MNaNO 3Solution is assembled into battery as electrolyte.The capacity of battery is 100mAh, with the rate charge-discharge of 0.4C, charging and discharging curve as shown in Figure 3,300 capacity that circulate do not have obvious decay.

Embodiment 3

Positive electrode adopts NaCoO 2The positive plate composition is pressed NaCoO 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 NaV 3O 8, cathode size is formed proportioning according to NaV 3O 8: 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.Adopt nonwoven fabrics as barrier film, use 1M Na 2SO 4The aqueous solution is assembled into battery as electrolyte.The capacity of battery is 160mAh, and with the rate charge-discharge of 0.5C, 300 capacity that circulate do not have obvious decay.

Embodiment 4

Positive electrode adopts NaVPO 4F.The positive plate composition is pressed NaVPO 4F: 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 NaV 3O 8, cathode size is formed proportioning according to NaV 3O 8: 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.Adopt nonwoven fabrics as barrier film, use 2M Na 2SO 4The aqueous solution is assembled into battery as electrolyte.The capacity of battery is 150mAh, and with the rate charge-discharge of 0.2C, 300 capacity that circulate do not have obvious decay.

Embodiment 5

Positive electrode adopts Na 3Fe 2(PO 4) 3The positive plate composition is pressed Na 3Fe 2(PO 4) 3: 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 NaV 3O 8, cathode size is formed proportioning according to NaV 3O 8: 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.Adopt nonwoven fabrics as barrier film, as electrolyte, be assembled into battery with the 6M NaCl aqueous solution.The capacity of battery is 140mAh, and with the rate charge-discharge of 1C, 400 capacity that circulate do not have obvious decay.

Embodiment 6

Positive electrode adopts synthetic Na 3V 2(PO 4) 3The positive plate composition is pressed Na 3V 2(PO 4) 3: 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 NaV 3O 8, cathode size is formed proportioning according to NaV 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.Adopt nonwoven fabrics as barrier film, use 2M Na 2SO 4The aqueous solution is assembled into battery as electrolyte.The capacity of battery is 100mAh, and with the rate charge-discharge of 0.5C, 300 capacity that circulate do not have obvious decay.

Claims (7)

1, a kind of water solution Na ion chargeable battery is made up of positive pole, negative pole, barrier film and electrolyte, it is characterized in that anodal adopt sodium ion to embed and taking off the relative high embedding of having of embedding/the take off material of current potential platform; Negative pole adopts sodium ion to embed and takes off the relative low embedding of having of embedding/the take off material of current potential platform; Electrolyte is the aqueous solution of compounds containing sodium.
2. water solution Na ion chargeable battery according to claim 1 is characterized in that described its positive electrode adopts oxide, sulfide, phosphide, chloride or phosphate, the sulfate of transition metal, or the dopant material of its metal or nonmetalloid.
3. water solution Na ion chargeable battery according to claim 1 is characterized in that described negative material adopts oxide, sulfide, phosphide, chloride or phosphate, the sulfate of transition metal, or the dopant material of its metal or nonmetalloid.
4. water solution Na ion chargeable battery according to claim 2 is characterized in that described positive electrode is one or more the mixture among NaMn2O4, NaCoO2, NaNiO2, NaCo1/3Ni1/3Mn1/3O2, NaMnO2, NaFePO4, NaV2O5 or the NaVPO4F.
5. water solution Na ion chargeable battery according to claim 3 is characterized in that described negative material is one or more the mixture among NaV3O8, VO2, MnO2, NaTiS2, NaMoS2, NaMoO2 or the NaWO3.
6. water solution Na ion chargeable battery according to claim 1, it is characterized in that described electrolyte is the aqueous solution of one or more mixtures in sodium sulphate, sodium halide, sodium nitrate, NaOH, sodium phosphate, sodium acetate or the sodium oxalate, the concentration of solution is 0.1mol/l-15mol/l.
7. according to the described water solution Na ion chargeable battery of claim 1, it is characterized in that in the described electrolyte, also add one or more the aqueous solution of mixture have in supporting electrolyte sulfate, nitrate, phosphate, acetate, oxalates, chloride, fluoride or the hydroxide; Its cation is the mixture of one or more ions in alkali metal, alkaline-earth metal, rare earth metal, aluminium, magnesium or the zinc.
CN 200710042919 2007-06-28 2007-06-28 A water solution Na ion chargeable battery CN101087018A (en)

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Cited By (16)

* Cited by examiner, † Cited by third party
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
CN102714302A (en) * 2009-12-24 2012-10-03 住友化学株式会社 Method for producing electrode, method for producing electrode paste, and sodium secondary battery
CN102701184A (en) * 2012-06-19 2012-10-03 武汉大学 Carbon negative electrode material of sodium ion battery
CN103022577A (en) * 2012-12-27 2013-04-03 武汉大学 Water system chargeable sodium-ion battery
CN103050682A (en) * 2012-12-24 2013-04-17 北京理工大学 Sodium ion battery electrode material and preparation method thereof
CN103107373A (en) * 2011-11-14 2013-05-15 苏州宝时得电动工具有限公司 Battery
CN103413979A (en) * 2013-07-30 2013-11-27 复旦大学 Charge-discharge battery taking zinc as negative pole
CN103597649A (en) * 2011-03-09 2014-02-19 亚奎尼能源公司 Metal free aqueous electrolyte energy storage device
CN104112858A (en) * 2014-06-26 2014-10-22 西南大学 Preparation method and application of network structure nano NaVPO4F/C composite material and application thereof
CN104319424A (en) * 2014-11-06 2015-01-28 中国科学技术大学 Water-system sodium ion battery as well as manufacturing method and application thereof
CN104505510A (en) * 2014-12-12 2015-04-08 吉林大学 Negative electrode material of sodium ion secondary batter, preparation method of negative electrode material, as well as sodium ion battery
CN104900875A (en) * 2015-05-15 2015-09-09 武汉理工大学 NaCuVO4 nanoparticles and preparation method and application thereof
CN105047913A (en) * 2015-05-22 2015-11-11 武汉大学 Method of preparing olivine-type sodium ferric phosphate through electrochemical method
CN106450295A (en) * 2016-09-14 2017-02-22 上海电力学院 Sodium-ion battery positive electrode material Na3Fe2(PO4)3 and preparation method thereof
CN107500355A (en) * 2017-08-30 2017-12-22 北京理工大学 A kind of preparation method for being layered lepidocrocite type nanometer strip vanadium dioxide
US9960397B2 (en) 2011-03-09 2018-05-01 Aquion Energy, Inc. Aqueous electrolyte energy storage device

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102714302A (en) * 2009-12-24 2012-10-03 住友化学株式会社 Method for producing electrode, method for producing electrode paste, and sodium secondary battery
CN102110839A (en) * 2009-12-29 2011-06-29 万向电动汽车有限公司 Battery
CN103597649B (en) * 2011-03-09 2016-05-25 亚奎尼能源公司 Metal-free aqueous electrolyte energy storing device
CN103597649A (en) * 2011-03-09 2014-02-19 亚奎尼能源公司 Metal free aqueous electrolyte energy storage device
US9960397B2 (en) 2011-03-09 2018-05-01 Aquion Energy, Inc. Aqueous electrolyte energy storage device
CN103107373A (en) * 2011-11-14 2013-05-15 苏州宝时得电动工具有限公司 Battery
CN103107373B (en) * 2011-11-14 2015-09-09 苏州宝时得电动工具有限公司 Battery
CN102701184A (en) * 2012-06-19 2012-10-03 武汉大学 Carbon negative electrode material of sodium ion battery
CN103050682A (en) * 2012-12-24 2013-04-17 北京理工大学 Sodium ion battery electrode material and preparation method thereof
CN103022577A (en) * 2012-12-27 2013-04-03 武汉大学 Water system chargeable sodium-ion battery
CN103413979A (en) * 2013-07-30 2013-11-27 复旦大学 Charge-discharge battery taking zinc as negative pole
CN104112858A (en) * 2014-06-26 2014-10-22 西南大学 Preparation method and application of network structure nano NaVPO4F/C composite material and application thereof
CN104319424A (en) * 2014-11-06 2015-01-28 中国科学技术大学 Water-system sodium ion battery as well as manufacturing method and application thereof
CN104505510A (en) * 2014-12-12 2015-04-08 吉林大学 Negative electrode material of sodium ion secondary batter, preparation method of negative electrode material, as well as sodium ion battery
CN104900875B (en) * 2015-05-15 2018-04-27 武汉理工大学 NaCuVO4Nano particle and its preparation method and application
CN104900875A (en) * 2015-05-15 2015-09-09 武汉理工大学 NaCuVO4 nanoparticles and preparation method and application thereof
CN105047913A (en) * 2015-05-22 2015-11-11 武汉大学 Method of preparing olivine-type sodium ferric phosphate through electrochemical method
CN105047913B (en) * 2015-05-22 2018-11-23 武汉大学 A kind of method that electrochemical process prepares olivine-type phosphoric acid ferrisodium
CN106450295A (en) * 2016-09-14 2017-02-22 上海电力学院 Sodium-ion battery positive electrode material Na3Fe2(PO4)3 and preparation method thereof
CN107500355A (en) * 2017-08-30 2017-12-22 北京理工大学 A kind of preparation method for being layered lepidocrocite type nanometer strip vanadium dioxide
CN107500355B (en) * 2017-08-30 2019-05-31 北京理工大学 A kind of preparation method being layered lepidocrocite type nanometer strip vanadium dioxide

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