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CN1674347A - Mixed aquo-lithium ion battery - Google Patents

Mixed aquo-lithium ion battery Download PDF

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Publication number
CN1674347A
CN1674347A CNA2005100252696A CN200510025269A CN1674347A CN 1674347 A CN1674347 A CN 1674347A CN A2005100252696 A CNA2005100252696 A CN A2005100252696A CN 200510025269 A CN200510025269 A CN 200510025269A CN 1674347 A CN1674347 A CN 1674347A
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lithium ion
battery according
electrolyte
electrode film
battery
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CN1328818C (en
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夏永姚
王永刚
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Beijing Enli Power Technology Co ltd
Enpower Energy Technology Co ltd
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Fudan University
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Priority to CNB2005100252696A priority Critical patent/CN1328818C/en
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Priority to PCT/CN2006/000711 priority patent/WO2006111079A1/en
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • H—ELECTRICITY
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    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
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    • H—ELECTRICITY
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • H01G11/58—Liquid electrolytes
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    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
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    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/145—Liquid electrolytic capacitors
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The present invention relates to a new-type high-performance mixed aquo system lithium ion cell. Said invention is characterized by that its positive electrode is made of intercalation compound electrode material containing lithium ion, and its negative electrode is made of the electrode materials of active carbon, mesopore carbon or carbon nano tube, etc, with high specific surface, and its electrolyte adopts aquo system electrolyte containing lithium ion. Said invention has longer circulation life, it is more than ten times that of general secondary cell, and has the features of high power, safety, low cost and free from environmental pollution.

Description

Mixed aquo-lithium ion battery
Technical field
The invention belongs to battery and capacitor technology field, be specifically related to a kind of novel high-performance mixed aquo-lithium ion battery.
Background technology
Along with economy constantly develops, must cause increasing the weight of of depletion of natural resources, environmental pollution and global greenhouse effects such as oil, coal.The human equilibrium relation that must hold between economic growth, environmental protection and the energy resource supply this Trinitarian " three E ".Now the consumption figure in energy every year is converted to oil and is about 8,000,000,000 tons in the world, and wherein 90% is fossil fuel.By present consumption speed, greatly just can be exhausted after 100 years to 200 years.The comprehensive high-efficiency development and utilization of new forms of energy, power-saving technology and green technology has become very urgent subject.The development electric automobile is imperative, countries in the world active development electric automobile, electrical source of power as electric automobile mainly contains secondary cell, electrochemical super-capacitor and fuel cell etc. now, and wherein secondary cell comprises lead acid accumulator, Ni-MH battery and lithium ion battery.But weigh from comprehensive face such as cost, fail safe, battery performance and environmental impact, do not have a kind of power supply can satisfy the requirement of electric powered motor power supply in the above-mentioned power supply.Though secondary cells such as lead acid accumulator, ni-mh, lithium ion have bigger energy density, cycle life is shorter, and high rate during charging-discharging is relatively poor; And the lead-acid battery specific energy is low, and is plumbous toxic; Existing lithium ion battery is owing to use organic electrolyte to have safety issue.Though existing electrochemical double layer capacitor has the long-life, high-output power, energy density is less than normal.(W/Kg) is less for fuel cell cost height and power output, the problems such as requirement of can not satisfy starting, quickening and climb.For solving the problems referred to above of existing power supply, Canada Moli Energy company (international patent WO95/21470) has proposed aquo-lithium ion battery, basic conception is similar to existing organic system lithium ion battery, and the regulation both positive and negative polarity all adopts lithium ion to embed compound, as LiMn 2O 4, VO 2, LiV 3O 8, FeOOH etc.But in the aqueous solution, liberation of hydrogen, oxygen evolution reaction can take place when lithium ion embeds to take off when reaching certain potentials in the embedding process, be difficult to find and lithium ion only takes place embed and take off embedding and liberation of hydrogen does not take place, analyse the electrode pair material of oxygen.And the negative material cycle performance of mentioning in the patent is relatively poor, and promptly the cyclicity of aquo-lithium ion battery is very poor, often can not be above tens times.
Summary of the invention
The objective of the invention is to propose a kind ofly have extended cycle life, power is big, cost is low, and the mixed aquo-lithium ion battery of non-environmental-pollution.
The aquo-lithium ion battery that the present invention proposes is made up of cathode film, negative electrode film, the barrier film between cathode film and negative electrode film and the electrolyte that contains zwitterion and have an ionic conductance.Wherein, described cathode film adopts lithium ion can embed and take off the material of embedding, for example can adopt oxide, sulfide, phosphide or the chloride etc. of transition metal to embed compound.Described negative electrode film adopts and contains ion and can adsorb material with desorption, for example can adopt porous structure materials such as active carbon, mesoporous carbon or carbon nano-tube with Large ratio surface, also can adopt above-mentioned material with loose structure and other that composite material of the material of pseudo-capacitance performance is arranged, other has the material of pseudo-capacitance performance to comprise embedding compound, the organic conductive macromolecule material of metal oxide, lithium ion or contains the material etc. of free radical.The described electrolyte that contains zwitterion is the aqueous solution that contains lithium ion.
Among the present invention, the electrolyte form can be solution, gel.Electrolyte is one or more the mixed aqueous solution that contains above-mentioned cationic sulfate, nitrate, phosphate, acetate, chloride or hydroxide etc.It is 2 mol-10 mol for concentration, and, pH value 〉=7 of electrolyte.
The electrolyte solution that contains zwitterion and have the ionic conductance performance of ion transport can be provided among the present invention, specifically can be Li 2SO 4, LiCl, LiNO 3, LiOH etc.For improving ionic conductivity and ion transport speed, also can add an amount of supporting electrolyte, as KCl, K 2SO 4Deng.Also can add an amount of filler in the electrolyte (as porous SiO 2Deng), make gelatinous electrolyte.
Among the present invention, the cation in the electrolyte comprises the lithium ion in the alkali metal, perhaps the mixture of one or more ions of lithium ion and otheralkali metal, alkaline-earth metal, rare earth metal, aluminium or zinc.
Among the present invention, the current collector material of cathode film, negative electrode film can be porous, the netted or thin-film material of metallic nickel, aluminium, stainless steel, titanium etc.
Among the present invention, consider the oxygen problem of analysing of the aqueous solution, the described embedding compound that is used as cathode film can adopt oxide, sulfide, phosphide or the chloride of manganese, nickel, cobalt, iron or vanadium, for example, and LiMn 2O 4, LiCoO 2, LiCo 1/3Ni 1/3Mn 1/3O 2, LiNiO 2, LiFePO 4, and the material that mixes of other metallic elements M of above-mentioned embedding compound, doped chemical M is one or more of Li, Mg, Cr, Al, Co, Ni, Mn, Al, Zn, Cu, La, its doping with respect to the mol ratio of base metal element smaller or equal to 50%.Consider cost and fail safe, adopt LiMn 2O 4And the LiM of other metallic elements M doping xMn 2-xO 4(M is one or more in the above-mentioned element, and mol ratio X usually≤0.5) is comparatively suitable.The electron conduction agent (as graphite, carbon black, acetylene black etc.) and the binding agent (weight≤20% is as poly-tetrem alkene, water-soluble rubber, cellulose etc.) that also can add an amount of (weight≤50%) in the described cathode film material.Above-mentioned composite material can be made into the slurry of certain viscosity.This slurry is coated on the electrode collector, obtains the anode electrode film.
Among the present invention, negative electrode film adopts active carbon, mesoporous carbon or CNT (carbon nano-tube) etc., and specific surface can be at 1000m 2More than/the g.For improving the electron conduction of electrode, also can add an amount of above-mentioned electron conduction agent.With above-mentioned composite material (raw material of wood-charcoal material, electron conduction agent and binding agent), make slurry, be coated on the electrode collector, obtain the negative electrode film.Consider that negative pole adopts active carbon, mesoporous carbon or the CNT (carbon nano-tube) material of single high-ratio surface, the specific energy density of electrode is lower, also can add the material that an amount of (≤50%) has the pseudo-capacitance performance in negative pole, for example: LiMn 2O 4, VO 2, LiV 3O 8, FeOOH or polyaniline etc., the current potential of these materials is generally between 2.5～3V.
Among the present invention, the porous septum that the barrier film between the positive and negative electrode can adopt existing aqoue seconary battery to use, as the fibreglass diaphragm that lead acid accumulator is used, the porous polyphenyl alkene barrier film that uses for nickel-hydrogen battery.
The shape of battery of the present invention can be made cylinder type, square and button type etc.Its shell can adopt the composite material of organic plastics, metal material or metallo organic material etc.
The basic functional principle of the lithium ion battery that the present invention proposes is as shown in Figure 1: to the battery of dressing up, at first must charge.In the charging process, lithium ion is deviate from from positive pole, and by electrolyte, lithium ion is adsorbed on the negative pole that materials such as activated carbon are made.In the discharge process, lithium ion desorption from the negative pole, by electrolyte, lithium ion embeds anodal.Charge and discharge process only relates to lithium ion in two interelectrode transfers.Therefore claim that battery of the present invention is a mixed aquo-lithium ion battery.Mixed aquo-lithium ion battery is different from the mixed type electrochemical super-capacitor, as C/NiOOH, and Li 4Ti 5O 12Systems such as/C, these systems charge and discharge in the process at capacitor, relate to zwitterion and react on electrode simultaneously, often cause the poorness of electrolyte.
The present invention adopts material as cathode such as active carbon, negative pole mainly is to utilize the Electrostatic Absorption mechanism of lithium ion on electrode, but not insertion reaction, on the one hand can be by the ratio of simple adjustment both positive and negative polarity active material, regulate the current potential of negative pole, make battery liberation of hydrogen, oxygen evolution reaction not take place at charge and discharge process; Absorption, the desorption good reversibility of lithium ion on negative pole on the other hand, cycle performance is very good.The mixed aquo-lithium ion battery average working voltage is 1.3V, and has very long cycle life, is more than ten times of common secondary cell, has overcome the problem of the cyclicity difference of aquo-lithium ion battery in the previous patent.Novel mixed aquo-lithium ion battery has long circulation life, and is high-power, the characteristics of safety, low cost and non-environmental-pollution.Be particularly suitable for electrical source of power as electric automobile.
Mixed aquo-lithium ion discharge of the present invention pond is that secondary cell (comprises lead acid accumulator, Ni-MH battery and lithium ion battery) and the combination of both technology of electrochemical super-capacitor, so the technology of preparing that is applicable to secondary cell and electrochemical super-capacitor all is applicable to the preparation of mixed aquo-lithium ion battery, the preparation technology's (film, press mold, slurry etc.) who comprises electrode, the shape of electrode (takeup type, stacked and spiral etc.), and irritate liquid and technology such as seal.
Description of drawings
Fig. 1 is the basic functional principle figure of mixed aquo-lithium ion battery.
The structure of the cylinder battery that Fig. 2 adopts.
The charging and discharging curve of Fig. 3 cylinder mixed aquo-lithium ion battery.
Embodiment
The present invention is further illustrated by embodiment down.
Embodiment 1:
Positive electrode adopts commercial Li-ion batteries spinel-type LiMn 2O 4Press LiMn anodal the composition 2O 4: carbon black: the part by weight mixed slurry of binding agent=80: 10: 10, evenly be coated on the nickel screen collector, be pressed into electrode after the oven dry.Negative material adopts commercial active carbon, and wet end furnish is according to active carbon: conductive agent: binding agent=mix slurry at 85: 5: 10, evenly be applied to then on the nickel screen collector, and be pressed into electrode after the oven dry.Among this embodiment, the positive electrode actual capacity is 80mAh/g, and negative pole is 40mAh/g, and anodal single face coating weight is 5mg/cm 2, negative pole is 10mg/cm 2Then two kinds of electrodes are cut according to specification, matched group is dressed up 2# battery (diameter is the high 50mm of being of 14mm*), and the barrier film that is adopted is the barrier film of commercial Ni-MH battery, and electrolyte is the Li of 2M 2SO 4Solution, the structure of battery as shown in Figure 2.Discharge curve as shown in Figure 3, at the 0V-1.8V operation interval, discharging current is 200mAh for the 1C capacity, average working voltage is 1.3V, the 10C capacity of charging and discharging maintains 190mAh, through 10000 times the circulation after, capability retention can have 90% (seeing table 1 for details).
Embodiment 2:
Positive electrode adopts commercial Li-ion batteries LiCoO 2, all the other mix slurry, coating electrode and cell preparation with embodiment 1 according to step among the embodiment 1 and condition.The positive electrode actual capacity is 120mAh/g, and negative pole is 40mAh/g, and anodal single face coating weight is 3.4mg/cm 2, negative pole is 10mg/cm 2At the 0V-1.8V operation interval, discharging current is 250mAh for the 2C capacity, and average working voltage is 1.2V, and the 10C capacity of charging and discharging maintains 240mAh, and after 10000 circulations, capability retention can have 87% (seeing table 1 for details).
Embodiment 3:
Positive electrode adopts commercial Li-ion batteries LiCo 1/3Ni 1/3Mn 1/3O 2, all the other mix slurry, coating electrode and cell preparation with embodiment 1 according to step among the embodiment 1 and condition.The positive electrode actual capacity is 100mAh/g, and negative pole is 40mAh/g, and anodal single face coating weight is 4mg/cm 2, negative pole is 10mg/cm 2At the 0V-1.8V operation interval, discharging current is 230mAh for the 1C capacity, and average working voltage is 1.0V, and the 10C capacity of charging and discharging maintains 210mAh, and after 10000 circulations, capability retention can have 92% (seeing table 1 for details).
Embodiment 4:
Positive electrode adopts commercial Li-ion batteries doped spinel type LiMg 0.2Mn 1.8O 4, all the other mix slurry, coating electrode and cell preparation with embodiment 1 according to step among the embodiment 1 and condition.The positive electrode actual capacity is 78mAh/g, and negative pole is 40mAh/g, and anodal single face coating weight is 5.5mg/cm 2, negative pole is 10mg/cm 2At the 0V-1.8V operation interval, discharging current is 190mAh for the 1C capacity, and average working voltage is 1.3V, and the 10C capacity of charging and discharging maintains 185mAh, and after 10000 circulations, capability retention can have 91% (seeing table 1 for details).
Embodiment 5:
Positive electrode adopts commercial Li-ion batteries LiMn 2O 4That negative pole adopts is commercial active carbon and LiV 3O 8Composite material (both mass ratioes are 2: 1), mix slurry, coating electrode and cell preparation according to step among the embodiment 1 and condition.The positive electrode actual capacity is 80mAh/g, and negative pole is 80mAh/g, and anodal single face coating weight is 10mg/cm 2, negative pole is 10mg/cm 2At the 0V-1.8V operation interval, discharging current is 300mAh for the 2C capacity,, average working voltage is 1.2V, and the 20C capacity of charging and discharging maintains 250mAh, and after 10000 circulations, capability retention can have 80% (seeing table 1 for details).
Embodiment 6:
Positive electrode all adopts the commercial active carbon of using, and mixes slurry, coating electrode and cell preparation according to step among the embodiment 1 and condition.The positive electrode actual capacity is 40mAh/g, and negative pole is 40mAh/g, and anodal single face coating weight is 10mg/cm 2, negative pole is 10mg/cm 2At the 0V-1.8V operation interval, discharging current is 100mAh for the 1C capacity, and average working voltage is 0.5V, and the 10C capacity of charging and discharging maintains 100mAh, and after 10000 circulations, capability retention can have 95% (seeing table 1 for details).
Table 1. adopts the performance of the mixed aquo-lithium ion battery of different positive and negative pole material preparations to compare.
Average working voltage V Capacity mAh (1C) Capacity mAh (10C) Capability retention (after 10000 times)
Embodiment 1 C/LiMn 2O 4 ??1.3 ????200 ????190 ????90％
Embodiment 2 C/LiCoO 2 ??1.2 ????250 ????240 ????87％
Embodiment 3 C/LiCo 1/3Ni 1/3Mn 1/3O 2 ??1.0 ????230 ????210 ????92％
Embodiment 4 C/LiMg 0.2Mn 1.8O 4 ??1.3 ????190 ????185 ????91％
Embodiment 5 (AC+LiV 3O 8)/LiMn 2O ????4 ??1.2 ????300 ????250 ????80％
Embodiment 6 AC/AC ??0.5 ????100 ????100 ????95％

Claims (9)

1、一种混合型水系锂离子电池，由正极膜、负极膜、介于两者之间的隔膜及含有阴阳离子并具有离子导电性的电解质组成，其特征在于所述正极膜采用锂离子嵌入化合物：过渡金属的氧化物、硫化物、磷化物或氯化物；所述负极膜采用多孔结构材料活性炭、介孔碳或碳纳米管，或者这些多孔结构材料和其它有准电容性能的材料的混合材料。电解质为含锂离子的水溶液。1. A hybrid aqueous lithium-ion battery, composed of a positive electrode film, a negative electrode film, a separator between the two, and an electrolyte containing anions and cations and having ion conductivity, characterized in that the positive electrode film adopts lithium ion intercalation Compounds: oxides, sulfides, phosphides or chlorides of transition metals; the negative electrode film uses porous structure materials activated carbon, mesoporous carbon or carbon nanotubes, or a mixture of these porous structure materials and other materials with quasi-capacitive properties Material. The electrolyte is an aqueous solution containing lithium ions. 2、根据权利要求1所述的电池，其特征在于所述电解质为硫酸盐、硝酸盐、磷酸盐、醋酸盐、氯化物或氢氧化物的一种或几种的混合水溶液，其为浓度为2摩尔/升-10摩尔/升。2. The battery according to claim 1, characterized in that the electrolyte is a mixed aqueous solution of one or more of sulfate, nitrate, phosphate, acetate, chloride or hydroxide, which is the concentration It is 2 mol/L-10 mol/L. 3、根据权利要求1所述的电池，其特征在于所述电解质，其阳离子包括碱金属中的锂离子，或者锂离子和其他碱金属、碱土金属、稀土金属、铝或锌的一种或几种离子的混合物。3. The battery according to claim 1, characterized in that the electrolyte, its cations include lithium ions in alkali metals, or one or more of lithium ions and other alkali metals, alkaline earth metals, rare earth metals, aluminum or zinc a mixture of ions. 4、根据权利要求1所述的电池，其特征在于所述过渡金属元素为锰、镍、钴、铁或钒。4. The battery according to claim 1, characterized in that the transition metal element is manganese, nickel, cobalt, iron or vanadium. 5、根据权利要求1所述的电池，其特征在于所述嵌入化合物为LiMn2O4、LiCoO2、LiCo1/3Ni1/3Mn1/3O2、LiNiO2或LiFePO4，以及上述嵌入化合物的其他金属元素M掺杂的材料，掺杂元素M为Li、Mg、Cr、Al、Co、Ni、Mn、Al、Zn、Cu、La的一种或几种。5. The battery according to claim 1, characterized in that the intercalation compound is LiMn 2 O 4 , LiCoO 2 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiNiO 2 or LiFePO 4 , and the above-mentioned A material doped with other metal elements M embedded in the compound, and the doping element M is one or more of Li, Mg, Cr, Al, Co, Ni, Mn, Al, Zn, Cu, La. 6、根据权利要求1所述的电池，其特征在于所述正极膜还加入有适量导电剂和粘结剂。6. The battery according to claim 1, characterized in that an appropriate amount of conductive agent and binder are added to the positive electrode film. 7、根据权利要求1所述的电池，其特征在于所述负极膜还加入有适量导电剂和粘结剂。7. The battery according to claim 1, characterized in that an appropriate amount of conductive agent and binder are added to the negative electrode film. 8、根据权利要求1所述的电池，其特征在于所述负极膜还加入有适量准电容性能材料：LiMn2O4、VO2、LiV3O8、FeOOH或聚苯胺。8. The battery according to claim 1, characterized in that the negative electrode film is also added with an appropriate amount of quasi-capacitive materials: LiMn 2 O 4 , VO 2 , LiV 3 O 8 , FeOOH or polyaniline. 9、根据权利要求1所述的电池，其特征在于所述电解质为Li2SO4、LiCl、LiNO3、LiOH的水溶液。9. The battery according to claim 1, characterized in that the electrolyte is an aqueous solution of Li 2 SO 4 , LiCl, LiNO 3 , LiOH.
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