CN101154745A - Hydrographical rechargeable lithium or sodium ion battery - Google Patents

Hydrographical rechargeable lithium or sodium ion battery Download PDF

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Publication number
CN101154745A
CN101154745A CNA2007100461760A CN200710046176A CN101154745A CN 101154745 A CN101154745 A CN 101154745A CN A2007100461760 A CNA2007100461760 A CN A2007100461760A CN 200710046176 A CN200710046176 A CN 200710046176A CN 101154745 A CN101154745 A CN 101154745A
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ion
lithium ion
electrolyte
battery
battery according
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夏永姚
罗加严
李峰
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Fudan University
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Fudan University
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    • 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

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Abstract

The invention belongs to electrochemical technical field, in particular to a novel high performance water system lithium ion battery. The invention adopts an ion embedding in-out mechanism used by an organic system lithium ion battery in an energy storage element which uses a water solution as an electrolyte. The embedding-in reaction ion mainly includes lithium ion composite and sodium ion composite. In the invention, the positive pole adopts a material containing the positive ion embedding-in composite while the negative pole adopts a shell structure material of LiTi2(PO4)3; the electrolyte adopts a water system electrolyte of the positive ion. The electric charging and discharging process only relates to the ion transfer between the two electrodes, and the invention can still has the characteristic of a rocking-chair type organic system lithium ion battery; the invention is of long cycling service life, big power, safety, low cost and no pollution, and is particularly suitable to be used as an ideal power battery of electric vehicle.

Description

A kind of water system can be filled lithium or sodium-ion battery
Technical field
The invention belongs to technical field of electrochemistry, be specifically related to a kind of novel high-performance water system chargeable lithium ion pond.
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 organic system 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 novel aquo-lithium ion chargeable battery of non-environmental-pollution.
The aquo-lithium ion chargeable 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 ion can embed, 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 to coat and embeds compound L iTi 2(PO 4) 3The nucleocapsid structure material, shell is charcoal, Al 2O 3, ZnO, CoO, SiO 2, TiO 2, NiO or LiPON, the quality of shell is the 5-45% of nucleocapsid structure material; Above-mentioned embedding compound comprises that also one of them is doped with the material of other metallic elements.In the described electrolyte that contains zwitterion, cation comprises the compound of lithium ion in the alkali metal or sodium ion etc.
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, the electrolyte form can be solution, gel or all solid state.If solution, then electrolyte is one or more the mixed aqueous solution that contains above-mentioned cationic sulfate, nitrate, phosphate, acetate, chloride or hydroxide etc.It is 1 mol-10 mol for concentration, and, pH value 〉=7 of electrolyte.
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, or conducting polymer.And the material that contains other metallic elements M doping in the above-mentioned embedding compound, doped chemical M is one or more of Li, Mg, Cr, Al, Co, Ni, Mn, Al, Zn, Cu, La ion, 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 that mixes with other metallic elements M xMn 2-xO 4(M is one or more in the above-mentioned element, and mol ratio is usually less than 0.5) is comparatively suitable.The electron conduction agent (as graphite, carbon black, acetylene black etc.) and the binding agent (weight is smaller or equal to 20%, as poly-tetrem alkene, water-soluble rubber, cellulose etc.) that also can add an amount of (weight is smaller or equal to 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 the LiTi of the nucleocapsid structure of carbon coating 2(PO 4) 3For improving the electron conduction of electrode, also can add an amount of above-mentioned electron conduction agent and binding agent.With above-mentioned composite material, make slurry, be coated on the electrode collector, obtain the negative electrode film.
Among the present invention, the porous septum that the barrier film between the positive and negative electrode can adopt existing water system 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 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 or contain the above-mentioned salt of sodium ion or alkali 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.
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 following (aquo-lithium ion battery) of the chargeable battery that the present invention proposes:, at first must charge to the battery of dressing up.In the charging process, lithium ion is deviate from from positive pole, and by electrolyte, lithium ion embeds negative pole.In the discharge process, lithium ion is deviate from from negative pole, and 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 the water system chargeable lithium ion battery.
The present invention adopts the LiTi of nucleocapsid structure 2(PO 4) 3Make negative pole, coat shell and both can reduce the evolving hydrogen reaction current potential, can reduce LiTi again 2(PO 4) 3Decay, guarantee the cycle performance of entire cell system.Only relate to a kind of ion in two interelectrode transfers at charge and discharge process, manufacture craft has greatly than organic system lithium ion battery to be simplified.Reduce the cost of lithium ion battery, improved the fail safe of lithium ion battery.Novel water system chargeable lithium ion battery average working voltage is 1.5V, and has long cycle life, has overcome the problem of the cyclicity difference of aquo-lithium ion battery in the previous patent.Novel water system chargeable 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.
Novel water system chargeable lithium ion battery of the present invention is that secondary cell (comprises lead acid accumulator, Ni-MH battery and lithium ion battery) expansion and the revolutionary advancement in field, therefore be applicable to that the technology of preparing of secondary cell is applicable to that all mixed aquo can charge and discharge the preparation of 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
The charging and discharging curve of the novel water system chargeable lithium ion battery of Fig. 1 cylinder battery.
Embodiment
The present invention is further illustrated by embodiment down.
Embodiment 1:
As a comparison case, negative material adopts LiTi 2(PO 4) 3, wet end furnish is according to LiTi 2(PO 4) 3: conductive agent: binding agent=mix slurry at 85: 5: 10, evenly be applied to then on the nickel screen collector, be pressed into electrode after the oven dry.Positive electrode adopts commercial with lithium ion battery spinel-type LiMn 2O 4Press LiMn anodal the composition 2O 4: carbon black: the part by weight mixed slurry of binding agent=85: 5: 10, evenly be coated on the nickel screen collector, be pressed into electrode after the oven dry.Among this embodiment, the positive electrode actual capacity is 80mAh/g, and negative pole is 95mAh/g, and anodal single face coating weight is 12mg/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 1M 2SO 4Solution.Discharge curve as shown in Figure 1, at the 0V-1.85V operation interval, discharging current is 44mAh/g for the 1C capacity, average working voltage is 1.5V, the 10C capacity of charging and discharging maintains 15mAh/g, through 100 times the circulation after, capability retention can have 30% (seeing table 1 for details).
Embodiment 2:
The method that adopts vapour deposition among the embodiment 1 LiTi 2(PO 4) 3Carry out coated modified carbon, its synthetic method is: with the LiTi of the coating of the carbon among the embodiment 2 2(PO 4) 3Material is a body, places tube furnace.With toluene is carbon source, and Ar gas is as source of the gas, and the control gaseous flow blasts the toluene steam in the tube furnace, and tube furnace temperature programming therebetween is to 800 ℃ of reaction temperatures, treats that furnace temperature reaches to cause temperature requiredly, and the control furnace temperature is at reaction temperature 600min.After cooling, through grinding, promptly get the LiTi that required carbon coats 2(PO 4) 3Material.The phosphorus content of composite material is 5wt% by the thermogravimetric analysis test.LiTi with the carbon coating 2(PO 4) 3Be negative material, all the other carry out cell preparation with embodiment 1 according to step among the embodiment 1 and condition.Among this embodiment, the positive electrode actual capacity is 90mAh/g, and negative pole is 80mAh/g, and anodal single face coating weight is 10mg/cm 2, negative pole is 11mg/cm 2At the 0V-1.85V operation interval, discharging current is 43mAh/g for the 1C capacity, and average working voltage is 1.5V, and the 10C capacity of charging and discharging maintains 32mAh/g, and after 100 circulations, capability retention can have 70% (seeing table 1 for details).With pure LiTi 2(PO 4) 3Compare the LiTi that the carbon that adopts CVD (Chemical Vapor Deposition) method to obtain coats 2(PO 4) 3, its surface is coated by the carbon-coating of hydrophobization, and this structure has been blocked LiTi 2(PO 4) 3Particle contacts with the direct of electrolyte, has therefore avoided LiTi in the charge and discharge process 2(PO 4) 3Decomposition.Simultaneously, the carbon-coating on surface has good electrical conductivity, has effectively reduced the internal resistance between material granule, and a lot of defectives are arranged between the carbon-coating, makes sodium ion or lithium ion be free to by carbon-coating and embedding/deviate from LiTi 2(PO 4) 3Lattice.(seeing table 1 for details)
Embodiment 3:
The method that adopts vapour deposition among the embodiment 1 LiTi 2(PO 4) 3Carry out coated modified carbon, the phosphorus content of composite material is 15wt% by the thermogravimetric analysis test.LiTi with the carbon coating 2(PO 4) 3Be negative material, all the other carry out cell preparation with embodiment 2 according to step among the embodiment 1 and condition.Among this embodiment, 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-1.85V operation interval, discharging current is 40mAh/g for the 1C capacity, and average working voltage is 1.5V, and the 10C capacity of charging and discharging maintains 34mAh/g, and after 100 circulations, capability retention can have 90% (seeing table 1 for details).
Embodiment 4:
The method that adopts vapour deposition among the embodiment 1 LiTi 2(PO 4) 3Carry out coated modified carbon, the phosphorus content of composite material is 45wt% by the thermogravimetric analysis test.LiTi with the carbon coating 2(PO 4) 3Be negative material, all the other carry out cell preparation with embodiment 2 according to step among the embodiment 1 and condition.Among this embodiment, 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 16mg/cm 2At the 0V-1.85V operation interval, discharging current is 30mAh/g for the 1C capacity, and average working voltage is 1.5V, and the 10C capacity of charging and discharging maintains 8mAh/g, and after 100 circulations, capability retention can have 98% (seeing table 1 for details).
Embodiment 4:
Positive electrode adopts commercial with lithium ion battery LiCoO 2, the LiTi that negative pole adopts the carbon among the embodiment 3 to coat 2(PO 4) 3, all the other mix slurry, coating electrode and cell preparation with embodiment 3 according to step among the embodiment 1 and condition.The positive electrode actual capacity is 120mAh/g, and negative pole is 80mAh/g, and anodal single face coating weight is 6.6mg/cm 2, negative pole is 10mg/cm 2At the 0V-1.8V operation interval, discharging current is 48mAh/g for the 1C capacity, and average working voltage is 1.4V, and the 10C capacity of charging and discharging maintains 38mAh/g, and after 100 circulations, capability retention can have 85% (seeing table 1 for details).
Embodiment 5:
Positive electrode adopts commercial with lithium ion battery LiCo 1/3Ni 1/3Mn 1/3O 2, the LiTi that negative pole adopts the carbon among the embodiment 3 to coat 2(PO 4) 3, all the other mix slurry, coating electrode and cell preparation with embodiment 3 according to step among the embodiment 1 and condition.The positive electrode actual capacity is 100mAh/g, and negative pole is 80mAh/g, and anodal single face coating weight is 8mg/cm 2, negative pole is 10mg/cm 2At the 0V-1.8V operation interval, discharging current is 45mAh/g for the 1C capacity, and average working voltage is 1.0V, and the 10C capacity of charging and discharging maintains 34mAh/g, and after 100 circulations, capability retention can have 88% (seeing table 1 for details).
Embodiment 6:
Positive electrode adopts commercial with lithium ion battery doping spinel-type LiMg 0.2Mn 1.8O 4, the LiTi that negative pole adopts the carbon among the embodiment 3 to coat 2(PO 4) 3, all the other mix slurry, coating electrode and cell preparation with embodiment 3 according to step among the embodiment 1 and condition.The positive electrode actual capacity is 78mAh/g, and negative pole is 80mAh/g, and anodal single face coating weight is 10.3mg/cm 2, negative pole is 10mg/cm 2At the 0V-1.85V operation interval, discharging current is 38mAh for the 1C capacity, and average working voltage is 1.5V, and the 10C capacity of charging and discharging maintains 34mAh/g, and after 100 circulations, capability retention can have 95% (seeing table 1 for details).
Embodiment 7:
The method that adopts collosol and gel among the embodiment 1 LiTi 2(PO 4) 3Carry out the oxide coating modification, its synthetic method is: with the LiTi of the coating of the carbon among the embodiment 1 2(PO 4) 3Material is a body, places Al (NO 3) 3, Zn (NO 3) 2, Co (NO 3) 2, Si (C 2H 5O) 4, Ti (C 2H 5O) 4, Ni (NO 3) 2, waiting and stir evaporate to dryness in the solution, temperature programming is to 800 ℃ of reaction temperatures, treats that furnace temperature reaches to cause temperature requiredly, and the control furnace temperature is at reaction temperature 600min.After cooling, through grinding, promptly get the LiTi that required oxide coats 2(PO 4) 3Material.With Al 2O 3The LiTi that coats 2(PO 4) 3Material is an example, and the oxide shell content of composite material is 5wt%.LiTi with the carbon coating 2(PO 4) 3Be negative material, all the other carry out cell preparation with embodiment 1 according to step among the embodiment 1 and condition.Among this embodiment, 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-1.85V operation interval, discharging current is 40mAh/g for the 1C capacity, and average working voltage is 1.5V, and the 10C capacity of charging and discharging maintains 30mAh/g, and after 100 circulations, capability retention can have 87% (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 100 times)
Embodiment 1 LiTi 2(PO 4) 3/LiMn 2O 4 1.5 44 15 30％
Embodiment 2 LiTi 2(PO 4) 3-C(5％)/LiMn 2O 4 1.5 43 33 70％
Embodiment 3 LiTi 2(PO 4) 3-C(15％)/LiMn 2O 4 1.5 40 34 90％
Embodiment 4 LiTi 2(PO 4) 3-C(45％)/LiMn 2O 4 1.5 30 8 98％
Embodiment 5 LiTi 2(PO 4) 3-C(15％)/LiCoO 2 1.2 48 38 85％
Embodiment 6 LiTi 2(PO 4) 3-C(15％)/LiCo 1/3Ni 1/3Mn 1/3 O 2 1.0 45 34 88％
Embodiment 7 LiTi 2(PO 4) 3-C(15％)/ LiMg 0.2Mn 1.8O 4 1.5 38 34 95％
Embodiment 8 LiTi 2(PO 4) 3-Al 2O 3(15％)/ n 2O 4 1.5 40 30 87％

Claims (8)

1. water system lithium or sodium-ion battery, form by cathode film, negative electrode film, marginal barrier film and the electrolyte that contains zwitterion and have an ionic conductivity, it is characterized in that described cathode film adopts lithium ion or sodium ion can embed and take off the embedding compound of embedding: the oxide of transition metal, sulfide, phosphide or chloride; Negative electrode film adopts to coat and embeds compound L iTi 2(PO 4) 3The nucleocapsid structure material, shell is charcoal, Al 2O 3, ZnO, CoO, SiO 2, TiO 2, NiO or LiPON, the quality of shell is the 5-45% of nucleocapsid structure material gross mass; In the described electrolyte, cation comprises the lithium ion in the alkali metal, composite and sodium ion composite.
2. battery according to claim 1 is characterized in that described electrolyte is one or more a mixed aqueous solution of sulfate, nitrate, phosphate, acetate, chloride or hydroxide, and it is 1 mol-10 mol for concentration.
3. battery according to claim 2 is characterized in that described transition metal is manganese, nickel, cobalt, iron, vanadium or titanium.
4. battery according to claim 1 is characterized in that described anodal embedding compound is LiMn 2O 4, LiCoO 2, LiCo 1/3Ni 1/3Mn 1/3O 2, LiNiO 2, LiFePO 4, LiSiPO 4, LiMnPO 4, LCoPO 4Or conducting polymer; Comprise also and contain the material that other metallic elements M mixes in the above-claimed cpd that doped chemical M is one or more of Li, Mg, Cr, Al, Co, Ni, Mn, Al, Zn, Cu, La ion.
5. battery according to claim 1 is characterized in that it is the LiTi of nucleocapsid structure that described negative pole embeds compound 2(PO 4) 3Comprise also and contain the material that other metallic elements M mixes in the above-claimed cpd that doped chemical M is one or more of Li, Mg, Cr, Al, Co, Ni, Mn, Al, Zn, Cu, La ion.
6. battery according to claim 1 is characterized in that described cathode film also adds conductive agent and binding agent are arranged.
7. battery according to claim 1 is characterized in that described negative electrode film also adds conductive agent and binding agent are arranged.
8. battery according to claim 1 is characterized in that described electrolyte is Li 2SO 4, LiCl, LiNO 3, LiOH, Na 2SO 4, NaCl, NaNO 3, NaOH, its concentration is 1 mol-10 mol.
CNA2007100461760A 2007-09-20 2007-09-20 Hydrographical rechargeable lithium or sodium ion battery Pending CN101154745A (en)

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