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CN101212048A - Anode material of Li-ion secondary battery and battery containing the same - Google Patents

Anode material of Li-ion secondary battery and battery containing the same Download PDF

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Publication number
CN101212048A
CN101212048A CNA2006101723003A CN200610172300A CN101212048A CN 101212048 A CN101212048 A CN 101212048A CN A2006101723003 A CNA2006101723003 A CN A2006101723003A CN 200610172300 A CN200610172300 A CN 200610172300A CN 101212048 A CN101212048 A CN 101212048A
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positive electrode
battery
active material
positive
materials
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沈晞
潘福中
万彩敏
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BYD Co Ltd
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BYD Co Ltd
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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 relates to an anode material for a lithium ion secondary battery. The anode material comprises anode active substance, a conductive agent and a caking agent, wherein the anode active substance comprises material A and material B. The material B is the oxide C of plated metal lithium and/or the oxide D of plated metal lithium which are coated and processed by the material A. The material A is the lithium phosphate slat with a olivine structure. The anode material can obviously improve the safety performance of the lithium ion secondary battery; the battery has a big capacity; the anode material has a good performance of charge and discharge for a big current, circulation and high temperature storage.

Description

A kind of positive electrode of lithium rechargeable battery and contain the battery of this positive electrode
Technical field
The present invention relates to a kind of positive electrode of lithium rechargeable battery, also relate to a kind of lithium rechargeable battery that contains this positive electrode.
Background technology
At present, the positive active material that adopts in the anode material for lithium-ion batteries makes the LiCoO that has with the most use 2, LiNiO 2Or LiMn 2O 4, but above-mentioned several positive active material is owing at high temperature decompose easily and produce a large amount of heats, thus bring bigger potential safety hazard to battery.Compare LiFePO with these several positive active materials 4Material has then had their advantage concurrently, has also that low cost, fail safe are good, multinomial advantages such as good stability, iron resource are abundant, asepsis environment-protecting, is suitable for very much lithium rechargeable battery.Owing to special olivine structural, yet its low electronic conductivity becomes the widely used bottleneck of this positive active material of inhibition to iron lithium phosphate as positive active material.
In order to improve the electronic conductivity of iron lithium phosphate, generally adopt methods such as ion doping and carbon coating as positive active material.
People such as G.X.Wang (Electrochimica Acta, 50, (2004) 443-447.) have proposed at LiFePO 4In the method for doped with Mg element, but the actual effect and not obvious of improving, and the specific capacity of positive electrode also can reduce much behind the magnesium-doped element.
US2002182497 discloses a kind of compound phosphorus oxygen of lithium iron that is used for the carbon containing of anode active material of lithium ion secondary battery, and the compound phosphorus oxygen of the lithium iron of this carbon containing contains with LiFePO 4Be the particle of the compound phosphorus oxygen of lithium iron of the olivine structural of basis, and by the compound particle of the subparticle of carbon containing.But the phenomenon that coating layer comes off appears in clad material easily in the loop test process, the unsalted surface that exposes easily and electrolyte generation irreversible reaction, thereby cause the cycle performance variation of battery; And the cladding process complexity, manufacturing cycle is long, the cost height, and the uniformity coefficient of coating and the amount of coating also are difficult to control.
CN1641912A discloses a kind of anode for lithium battery, comprise LiMn2O4, conductive agent, adhesive and be used as the active material of arranging in pairs or groups, wherein, described conductive agent comprises a kind of in carbon nano-tube, nano-silver powder, acetylene black, graphite powder, the carbon black at least, described adhesive comprises a kind of in polytetrafluoroethylene, the polyvinylidene fluoride at least, and described active material as collocation comprises a kind of in cobalt acid lithium, lithium nickelate, lithium nickel cobalt dioxide, nickel LiMn2O4, LiFePO4, lithium manganese phosphate, the cobalt phosphate lithium at least.Lithium manganate material in this positive pole at high temperature very easily reacts the Mn of dissolving with electrolyte 2+Ion is at the negative material surface deposition, hinder the migrating channels of lithium ion, the chemical property variation of battery, can not be and simply lithium manganate material is mixed with other positive electrode from dealing with problems in essence, materials such as the LiFePO4 of arranging in pairs or groups in addition can not stop contacting of LiMn2O4 and electrolyte.Though therefore should can make battery obtain heavy-current discharge performance by positive pole, the security performance of battery be lower.
Summary of the invention
Can make battery obtain heavy-current discharge performance though the objective of the invention is to overcome above-mentioned anode for lithium battery of the prior art, but the defective that the security performance of battery is lower, provide a kind of battery that both can make to obtain heavy-current discharge performance, and make the positive electrode of the higher lithium rechargeable battery of the security performance of battery.
The invention provides a kind of positive electrode of lithium rechargeable battery, this positive electrode contains positive active material, conductive agent and binding agent, wherein, described positive active material contains materials A and material B, described material B is to coat transition metal lithium oxide C shown in the formula of handling (2) and/or the transition metal lithium oxide D shown in the formula (3) by materials A, and described materials A is the phosphate metal lithium salts with olivine structural shown in the formula (1):
Li 1+aL bPO 4 (1)，
Wherein ,-0.1≤a≤0.2,0.9≤b≤1.1, L is at least a in iron, aluminium, titanium, cobalt, boron, chromium, nickel, magnesium, zirconium, gallium, vanadium, manganese and the zinc;
Li 1+xNi 1-y-zMn yCo zM pO 2 (2)，
Wherein ,-0.1≤x≤0.2,0≤y≤1,0≤z≤1,0≤y+z≤1.0,0≤p≤0.2, M is at least a in boron, magnesium, aluminium, titanium, chromium, iron, zirconium, copper, zinc, gallium, yttrium, fluorine, iodine and the sulphur;
Or Li 1+mMn nN 2-nO 4(3),
Wherein ,-0.1≤m≤0.2,1.7≤n≤2.0, N is at least a in boron, magnesium, aluminium, titanium, chromium, iron, cobalt, zirconium, nickel, copper, zinc, gallium, yttrium, fluorine, iodine and the sulphur.
The present invention also provides a kind of lithium rechargeable battery, this battery comprises battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in the battery container, the electrode group comprises reels or stacked positive plate, barrier film and negative plate successively, described positive plate contains conducting base and is coated in the positive electrode on this conducting base two sides, wherein, described positive electrode is a positive electrode provided by the invention.
Adopt positive electrode provided by the invention, both can make lithium rechargeable battery obtain heavy-current discharge performance, and make the security performance of battery higher, and can make lithium rechargeable battery have the high power capacity of improvement, excellent cycle performance and storge quality.
Adopt positive electrode provided by the invention to have the following advantages:
1, the positive active material that adopts materials A of the present invention to mix with material B, coat the material B of transition metal lithium oxide C and/or transition metal lithium oxide D with materials A, has high conduction performance, can more effectively improve the electronic conductivity of positive electrode, make positive electrode can give play to height ratio capacity, and have better high rate during charging-discharging.And coat the coating layer difficult drop-off of transition metal lithium oxide C and/or transition metal lithium oxide D with materials A, structure and change in volume reduce in charge and discharge process, thermal stability improves, and can avoid transition metal lithium oxide C and/or transition metal lithium oxide D directly to contact with electrolyte, make battery have better cycle charge discharge electrical property and security performance.
2, by in positive electrode of the present invention, using conductive agent, can further improve the electronic conductivity of positive electrode, and can effectively be suppressed in the LiFePO4 and to add after the material B, the variation of active material and conductive agent contact condition in the loop test process that occurs easily owing to the difference of positive active material doff lithium volumetric expansion contraction, the cycle performance of battery and high-temperature storage performance have obtained great lifting.
Embodiment
The positive electrode of lithium rechargeable battery provided by the invention contains, positive active material, conductive agent and binding agent, wherein, described positive active material contains materials A and material B, described materials A is the phosphate metal lithium salts with olivine structural shown in the formula (1), and described material B is to coat transition metal lithium oxide C shown in the formula of handling (2) and/or the transition metal lithium oxide D shown in the formula (3) by materials A:
Li 1+aL bPO 4 (1)，
Wherein ,-0.1≤a≤0.2,0.9≤b≤1.1, L is at least a in iron, aluminium, titanium, cobalt, boron, chromium, nickel, magnesium, zirconium, gallium, vanadium, manganese and the zinc;
Li 1+xNi 1-y-zMn yCo zMpO 2 (2)，
Wherein ,-0.1≤x≤0.2,0≤y≤1,0≤z≤1,0≤y+z≤1.0, M is at least a in boron, magnesium, aluminium, titanium, chromium, iron, zirconium, copper, zinc, gallium, yttrium, fluorine, iodine and the sulphur;
Or Li 1+mMn nN 2-nO 4(3),
Wherein ,-0.1≤m≤0.2,1.7≤n≤2.0, N is at least a in boron, magnesium, aluminium, titanium, chromium, iron, cobalt, zirconium, nickel, copper, zinc, gallium, yttrium, fluorine, iodine and the sulphur.
According to positive electrode provided by the invention, in the preferred case, the particle mean size of described materials A is the 1-10 micron, and the particle mean size of described material B is the 5-14 micron.
According to positive electrode provided by the invention, in the preferred case, in described positive electrode, the weight ratio of materials A and described material B described in the described positive active material is 9.5: 0.5-0.5: 9.5, be preferably 7: 3-3: 7, the content of described conductive agent is the 2-20 weight % of described positive active material total amount, is preferably 3-15 weight %, the content of described binding agent is the 0.01-8 weight % of described positive active material total amount, is preferably 1-5 weight %.
According to positive electrode provided by the invention, the materials A shown in the formula (1) is preferably LiFePO 4Transition metal lithium oxide C shown in the formula (2) is preferably LiCoO 2Transition metal lithium oxide D shown in the formula (3) is preferably LiMn 2O 4
According to positive electrode provided by the invention, under the preferable case, in described material B, the weight ratio of described materials A and transition metal lithium oxide C and/or transition metal lithium oxide D is 0.0001-0.1, is preferably 0.001-0.05.
Described materials A can be commercially available or adopt known method to prepare.
The preparation method of described material B can adopt the liquid phase method for coating of hydro thermal method, sol-gel process, coprecipitation, oxidation-reduction method, obtains with coating source coating transition metal lithium oxide C and/or transition metal lithium oxide D.The slurries of lithium salts, phosphate and ferrous salt are contained in the coating source of adopting, and lithium salts wherein is as in lithium phosphate, lithium carbonate, lithium hydroxide, lithium oxalate and the lithium acetate one or more; Phosphate is as in ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and the lithium phosphate one or more; Ferrous salt, one or more as ferrous oxalate, ferrous acetate, frerrous chloride, ferrous sulfate, ferrous phosphate and hypophosphite monohydrate in ferrous.
Under the preferable case, the preparation method of described material B comprises, in water or organic solvent above-mentioned coating source and transition metal lithium oxide C and/or D powder evenly mixed; Perhaps earlier must coat presoma with above-mentioned coating source is mixed in water or organic solvent, add transition metal lithium oxide C and/or D powder again and fully mix.After the solvent evaporated, at 300-900 ℃ of roasting 1-24 hour, cooling obtained material B.
According to positive electrode provided by the invention, coat the material B of transition metal lithium oxide C and/or transition metal lithium oxide D with materials A, has high conduction performance, can more effectively improve the electronic conductivity of positive electrode, make positive electrode can give play to height ratio capacity, and have better high rate during charging-discharging.And coat the coating layer difficult drop-off of transition metal lithium oxide C and/or transition metal lithium oxide D with materials A, structure and change in volume reduce in charge and discharge process, thermal stability improves, and can avoid transition metal lithium oxide C and/or transition metal lithium oxide D directly to contact with electrolyte, make battery have better cycle charge discharge electrical property and security performance.
According to positive electrode provided by the invention, described conductive agent can adopt any conductive agent known in the field, for example can adopt in graphite, carbon fiber, carbon black, metal dust and the fiber one or more.
By in positive electrode of the present invention, using conductive agent, can further improve the electronic conductivity of positive electrode, and can effectively be suppressed in the LiFePO4 and to add after the material B, the variation of active material and conductive agent contact condition in the loop test process that occurs easily owing to the difference of positive active material doff lithium volumetric expansion contraction, the cycle performance of battery and high-temperature storage performance have obtained great lifting.
According to positive electrode provided by the invention, described binding agent can adopt any binding agent known in the field, for example can adopt in polyvinylidene fluoride, polytetrafluoroethylene or the butadiene-styrene rubber one or more.
Lithium rechargeable battery provided by the invention, comprise battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in the battery container, the electrode group comprises reels or stacked positive plate, barrier film and negative plate successively, described positive plate contains conducting base and is coated in the positive electrode on this conducting base two sides, wherein, described positive electrode is a positive electrode provided by the invention.
According to lithium rechargeable battery provided by the invention, wherein, described positive plate contains conducting base and is coated in the positive electrode on this conducting base two sides, and described conducting base is conventionally known to one of skill in the art, for example can be selected from aluminium foil, Copper Foil or various Punching steel strip.
The positive plate of lithium rechargeable battery of the present invention can adopt the known existing method preparation of those skilled in the art.For example, the preparation method of conventional positive plate comprises, positive active material, binding agent and conductive agent are become slurries with solvent, applies these slurries then on the wide cut conducting base, and then dry, rolling is also cut, and obtains positive plate.
In described method, the solvent that mixes with positive active material, binding agent and conductive agent can be selected from and well known to a person skilled in the art conventional solvent, as being selected from N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols one or more.The consumption of solvent can be coated on the described conducting base described slurry and gets final product.In general, it is 40-90 weight % that the consumption of solvent makes the content of positive active material in the slurries, is preferably 50-85 weight %.
Condition dry and roll-in is known in those skilled in the art, and for example the temperature of dry positive plate is generally 60-120C, and preferred 80-110 ℃, be 0.5-5 hour drying time.
According to lithium rechargeable battery provided by the invention, the structure of described electrode group is conventionally known to one of skill in the art, and in general, described electrode group comprises reels or stacked positive plate, barrier film and negative plate successively, and barrier film is between positive plate and negative plate.Coiling or stacked mode are conventionally known to one of skill in the art.
Described negative pole adopts known negative pole in this area, promptly contains negative current collector and the negative electrode material layer that is coated on this negative current collector.Anticathode material layer of the present invention has no particular limits, and is the same with prior art, and described negative electrode material layer generally includes the conductive agent that negative electrode active material, binding agent and selectivity contain.Described negative electrode active material can adopt various negative electrode active materials commonly used in the prior art, for example material with carbon element.Described material with carbon element can be non-graphitized charcoal, graphite or the charcoal that obtained by high-temperature oxydation by polyyne family macromolecule material, also can use other material with carbon element for example pyrolytic carbon, coke, organic polymer sinter, active carbon etc.Described organic polymer sinter can be by the product with gained after sintering such as phenolic resins, epoxy resin and the charing.
Described negative pole can be the various binding agents that are used for lithium ion secondary battery negative pole in the prior art with binding agent, and preferred described binding agent is the mixture of hydrophobicity binding agent and hydrophilic agglomerant.The ratio of described hydrophobicity binding agent and hydrophilic agglomerant has no particular limits, and can determine according to actual needs, and for example, the part by weight of hydrophilic agglomerant and hydrophobicity binding agent can be 0.3: 1-1: 1.Described binding agent can use with the aqueous solution or emulsion form, also can use with solid form, preferably use with the aqueous solution or emulsion form, have no particular limits the concentration of described hydrophilic agglomerant solution and the concentration of described hydrophobicity binding agent emulsion this moment, can adjust flexibly this concentration according to the viscosity of the cathode size slurry coating that will prepare and the requirement of operability, the concentration of for example described hydrophilic agglomerant solution can be 0.5-4 weight %, and the concentration of described hydrophobicity binding agent emulsion can be 10-80 weight %.Described hydrophobicity binding agent can be polytetrafluoroethylene or butadiene-styrene rubber or their mixture.Described hydrophilic agglomerant can be in hydroxypropyl methylcellulose, sodium carboxymethylcellulose, hydroxyethylcellulose or the polyvinyl alcohol one or more.
Negative material provided by the invention can also optionally contain the common conductive agent that contains in the prior art negative material.Because conductive agent is used to increase the conductivity of electrode, reduce the internal resistance of battery, so the present invention preferably contains conductive agent.The content of described conductive agent and kind are conventionally known to one of skill in the art, for example, are benchmark with the negative material, and the content of conductive agent is generally 0.1-12 weight %.Described conductive agent can be selected from one or more in conductive carbon black, nickel powder, the copper powder.
The preparation method of negative pole can adopt the whole bag of tricks known in the field, for example the conductive agent that negative electrode active material, binding agent and selectivity is contained with solvent is prepared into the negative material slurry, the addition of solvent is known in those skilled in the art, and the viscosity that can be coated with according to the slurry of the cathode size that will prepare and the requirement of operability are adjusted flexibly.Then prepared negative material slurry slurry is coated in dry compressing tablet on the negative electrode collector, cut-parts obtain negative pole again.The temperature of described drying is generally 120 ℃, and be generally 5 hours drying time.
The used solvent of described cathode size can be an all kinds of solvents of the prior art, and as water, water-soluble solvent or their mixture, described water-soluble solvent comprises that carbon number is lower alcohol, acetone, the N of 1-6, dinethylformamide etc.
According to lithium rechargeable battery provided by the invention, membrane layer is arranged between positive pole and the negative pole, has electrical insulation capability and liquid retainability energy.Described membrane layer can be selected from and well known to a person skilled in the art various membrane layers used in the lithium rechargeable battery, for example polyolefin micro porous polyolefin membrane, polyethylene felt, glass mat or ultra-fine fibre glass paper.
According to lithium rechargeable battery provided by the invention, electrolyte is nonaqueous electrolytic solution.Described nonaqueous electrolytic solution is the solution that electrolyte lithium salt forms in nonaqueous solvents, can use the nonaqueous electrolytic solution of routine well known by persons skilled in the art.Can be selected from lithium hexafluoro phosphate (LiPF such as electrolyte lithium salt 6), lithium perchlorate (LiClO 4), LiBF4 (LiBF 4), hexafluoroarsenate lithium (LiAsF 6), hexafluorosilicic acid lithium (LiSiF 6), tetraphenyl lithium borate (LiB (C 6H 5) 4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl 4) and fluorocarbon based sulfonic acid lithium (LiC (SO 2CF 3) 3), LiCH 3SO 3, LiN (SO 2CF 3) 2In one or more.Nonaqueous solvents can be selected from chain acid esters and ring-type acid esters mixed solution, wherein the chain acid esters can be fluorine-containing for dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other, sulfur-bearing or contain in the chain organosilane ester of unsaturated bond one or more.The ring-type acid esters can (γ-BL), sultone and other be fluorine-containing, sulfur-bearing or contain in the ring-type organosilane ester of unsaturated bond one or more for ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton.In described nonaqueous electrolytic solution, the concentration of electrolyte lithium salt is generally the 0.1-2 mol, is preferably the 0.8-1.2 mol.
According to lithium rechargeable battery provided by the invention, the preparation method of this battery is as well known to those skilled in the art, in general, the preparation method of this battery comprises the electrode group is inserted in the battery case, add electrolyte, sealing obtains lithium rechargeable battery then.Wherein, the method for sealing, the consumption of electrolyte is conventionally known to one of skill in the art.
The following examples will the invention will be further described.
Embodiment 1
Fe weight is accounted for LiCoO 20.1 the FeSO of weight % 4And H 3PO 4, LiOH is dissolved in the water according to 1: 1: 3 mixed in molar ratio, adds LiCoO 2Powder mixes, solvent evaporated, and then 700 ℃ of heat treatments 6 hours, it is 10 microns clad material LiCoO that cooling obtains particle mean size 2/ LiFePO 4
With PVDF by 1: 10 ratio solvent in NMP, with LiFePO 4(particle mean size is 5 microns), LiCoO 2/ LiFePO 4Clad material, graphite and carbon black add in this solution, fully are mixed and made into slurry, and it consists of LiFePO 4: (LiCoO 2/ LiFePO 4): (graphite+carbon black): PVDF=70: 30: (6+3): 5.This slurry is coated on equably on 20 microns the aluminium foil, in 120 ℃ dry down, obtain 450 * 42 * 170 millimeters positive plate after cutting, rolling, contain 5 gram positive active material (LiFePO in this positive plate 4+ (LiCoO 2/ LiFePO 4)).
With PVDF by 1: 10 ratio solvent in NMP, Delanium is added in this solution, fully be mixed and made into slurry, it consists of Delanium: PVDF=100: 5.Again this slurry is coated on equably on 20 microns the Copper Foil, 120 ℃ dry down, obtain 470 * 45 * 120 millimeters negative plate after the calendering, contain 2.5 gram Delaniums in this negative plate.
The polypropylene screen of above-mentioned positive and negative plate and 25 micron thickness is wound into the pole piece of a square lithium ion battery and is accommodated in the rectangular cell shell, subsequently with LiPF 6Be dissolved in by the concentration of 1 mol that formed electrolyte injects battery case in the mixed solvent of ethylene carbonate/dimethyl carbonate (EC/DMC)=1: 1, sealing, make thick 5 millimeters, wide 34 millimeters, high 50 millimeters square lithium ion battery, this battery size is LP053450A, and capacity is 720mAh.
Comparative example 1
According to the method identical with embodiment 1, that different is the LiFePO that consists of of positive electrode 4: graphite: PVDF=100: 9: 5.
Embodiment 2
According to the method identical with embodiment 1, that different is the LiFePO that consists of of positive electrode 4: (LiCoO 2/ LiFePO 4): (graphite+carbon black): PVDF=90: 10: (6+3): 5, LiFePO 4Particle mean size be 9 microns, LiCoO 2/ LiFePO 4Particle mean size be 13 microns.
Embodiment 3
According to the method identical with embodiment 1, different that be in the material B to be coated is LiMn 2O 4Powder, and positive electrode consist of LiFePO 4: (LiMn 2O 4/ LiFePO 4): (graphite+carbon black): PVDF=70: 30: (6+3): 5, LiFePO 4Particle mean size be 2 microns, LiMn 2O 4/ LiFePO 4Particle mean size be 6 microns.
Embodiment 4
According to the method identical with embodiment 1, different is that conductive agent is graphite and metal dust, and positive electrode consist of LiFePO 4: (LiCoO 2/ LiFePO 4): (graphite+metal dust): PVDF=70: 30: (2+1): 5.
Embodiment 5
According to the method identical with embodiment 1, different is that conductive agent is carbon black and carbon fiber, positive electrode consist of LiFePO 4: (LiCoO 2/ LiFePO 4): (carbon black+carbon fiber): PVDF=30: 70: (6+3): 5.
Embodiment 6
According to the method identical with embodiment 1, different is that conductive agent is carbon black and metallic fiber, positive electrode consist of LiFePO 4: (LiCoO 2/ LiFePO 4): (carbon black+metallic fiber): PVDF=70: 30: (7+5): 5.
Embodiment 7
According to the method identical with embodiment 1, that different is the LiFePO that consists of of positive electrode 4: (LiCoO 2/ LiFePO 4): (graphite+carbon black): PVDF=70: 30: (1+4): 5.
Embodiment 8
According to the method identical with embodiment 1, that different is the LiFePO that consists of of positive electrode 4: (LiCoO 2/ LiFePO 4): (graphite+carbon black): PVDF=60: 40: (1.5+1): 5.
The battery behavior test
1, volume test
Battery with embodiment and comparative example under the normal temperature lies prostrate with 1C milliampere current charges to 3.8 respectively, rises to 3.8 volts of backs with constant-potential charge at voltage, and cut-off current is the 0.05C milliampere, shelves 5 minutes; Battery was shelved 5 minutes with 1C milliampere current discharge to 2.0 volt.Obtain the capacity of battery normal temperature 1C milliampere current discharge to 2.0 volt, the battery capacity of each embodiment and comparative example is listed in the table 1.
Table 1
Battery capacity (Milliampere Hour) Capacity sustainment rate (%)
Embodiment 1 738 88.6
Comparative example 1 620 74.0
Embodiment 2 718 89.5
Embodiment 3 722 86.4
Embodiment 4 729 88.7
Embodiment 5 750 86.4
Embodiment 6 732 90.2
Embodiment 7 750 89.6
Embodiment 8 690 80.1
2, high temperature cyclic performance test
Under 60 ℃ of conditions, embodiment and comparative example battery are lied prostrate with 1C milliampere current charges to 3.8 respectively, rise to 3.8 volts of backs with constant-potential charge at voltage, cut-off current is the 0.05C milliampere, shelves 5 minutes; Battery was shelved 5 minutes with 1C milliampere current discharge to 2.0 volt.Repeat above step 300 time, obtain the capacity of 300 circulation backs of battery 1C milliampere current discharge to 2.0 volt, capacity sustainment rate before and after the computation cycles, the capacity sustainment rate of embodiment and comparative example is listed in the table 1.
3, high-temperature storage performance test
Under the room temperature condition, embodiment and comparative example battery respectively with 1C milliampere current charges to 3.8 volt, are risen to 3.8 volts afterwards with constant-potential charge at voltage, cut-off current is the 0.05C milliampere, shelve 5 minutes after, accurately measure cell thickness; Then above-mentioned battery is stored a week under 60 ℃ of conditions, measure the capacity of battery with 1C milliampere current discharge to 2.0 volt, and measure cell thickness once more, and counting cell capacity sustainment rate and change value of thickness, the capacity sustainment rate and the change value of thickness of embodiment and comparative example are listed in the table 2.
Table 2
Capacity sustainment rate (%) Change value of thickness (millimeter) 3C/0.2C discharge ratio (%) 5C/0.2C discharge ratio (%) Stove heat test 1 hour The battery surface maximum temperature (℃)
Embodiment 1 95.2 0.04 97.5 93.5 No change 165
Comparative example 1 80.5 0.13 78.9 52.7 Venting is opened after 41 minutes 182
Embodiment 2 95.2 0.04 90.1 86.7 No change 163
Embodiment 3 88.3 0.10 98.0 84.2 No change 162
Embodiment 4 94.4 0.06 98.4 94.0 No change 163
Embodiment 5 95.4 0.06 96.4 92.8 Venting is opened after 58 minutes 175
Embodiment 6 96.7 0.05 97.0 93.0 No change 163
Embodiment 7 95.0 0.04 95.3 90.6 No change 168
Embodiment 8 92.5 0.07 89.1 82.5 Venting is opened after 52 minutes 175
4, heavy-current discharge performance test
Under the room temperature condition, embodiment and comparative example battery are lied prostrate with 1C milliampere current charges to 3.8 respectively, rise to 3.8 volts of backs with constant-potential charge at voltage, cut-off current is the 0.05C milliampere, after shelving 5 minutes, battery was shelved 5 minutes with 0.2C milliampere current discharge to 2.0 volt, obtained the capacity of battery normal temperature 0.2C milliampere current discharge to 2.0 volt; Repeat then above-mentioned charge step again with battery respectively with the current discharge of 3C milliampere and 5C milliampere, obtain the capacity of battery normal temperature 3C milliampere and 5C milliampere current discharge to 2.0 volt, calculate the discharge capacity ratio of battery under the different electric currents.In embodiment and the comparative example under the different electric currents discharge capacity ratio of battery list in the table 2.
5, security performance test
Under the room temperature condition, embodiment and comparative example battery are lied prostrate with 1C milliampere current charges to 3.8 respectively, rise to 3.8 volts of backs with constant-potential charge at voltage, cut-off current is the 0.05C milliampere, shelves 5 minutes; Carry out the test of 160 ℃ of stove heat, the observation battery had no abnormal after 1 hour, and measured the maximum temperature of battery surface, and the observation situation of embodiment and comparative example and the maximum temperature of battery surface are listed in the table 2.
The test result of above table 1 and table 2 shows, adopt positive electrode of the present invention that the security performance of lithium rechargeable battery is improved significantly, and the capacity of battery is very big, and has excellent high rate during charging-discharging, cycle performance and high-temperature storage performance.

Claims (9)

1. the positive electrode of a lithium rechargeable battery, this positive electrode contains positive active material, conductive agent and binding agent, it is characterized in that, described positive active material contains materials A and material B, described material B is that described materials A is the phosphate metal lithium salts with olivine structural shown in the formula (1) by transition metal lithium oxide C shown in the formula (2) of materials A coating and/or the transition metal lithium oxide D shown in the formula (3):
Li 1+aL bPO 4 (1)，
Wherein ,-0.1≤a≤0.2,0.9≤b≤1.1, L is at least a in iron, aluminium, titanium, cobalt, boron, chromium, nickel, magnesium, zirconium, gallium, vanadium, manganese and the zinc;
Li 1+xNi 1-y-zMn yCo zM pO 2 (2)，
Wherein ,-0.1≤x≤0.2,0≤y≤1,0≤z≤1,0≤y+z≤1.0,0≤p≤0.2, M is at least a in boron, magnesium, aluminium, titanium, chromium, iron, zirconium, copper, zinc, gallium, yttrium, fluorine, iodine and the sulphur;
Or Li 1+mMn nN 2-nO 4(3),
Wherein ,-0.1≤m≤0.2,1.7≤n≤2.0, N is at least a in boron, magnesium, aluminium, titanium, chromium, iron, cobalt, zirconium, nickel, copper, zinc, gallium, yttrium, fluorine, iodine and the sulphur.
2. positive electrode according to claim 1, wherein, the particle mean size of described materials A is the 1-10 micron, the particle mean size of described material B is the 5-14 micron.
3. positive electrode according to claim 1, wherein, weight ratio in materials A described in the described positive active material and described material B is 9.5: 0.5-0.5: 9.5, the content of described conductive agent is the 2-20 weight % of described positive active material total amount, and the content of described binding agent is the 0.01-8 weight % of described positive active material gross weight.
4. positive electrode according to claim 3, wherein, the weight ratio of materials A and described material B described in the described positive active material is 7: 3-3: 7, the content of described conductive agent is the 3-15 weight % of described positive active material total amount, and the content of binding agent is the 1-5 weight % of described positive active material gross weight.
5. positive electrode according to claim 1, wherein, in described material B, the weight ratio of described materials A and transition metal lithium oxide C and/or transition metal lithium oxide D is 0.0001-0.1.
6. positive electrode according to claim 4, wherein, in described material B, the weight ratio of described materials A and transition metal lithium oxide C and/or transition metal lithium oxide D is 0.001-0.05.
7. according to claim 1,3 or 4 described positive electrodes, wherein, described conductive agent is one or more in graphite, carbon fiber, carbon black, metal dust and the fiber.
8. according to claim 1,3 or 4 described positive electrodes, wherein, described binding agent is one or more in polyvinylidene fluoride, polytetrafluoroethylene or the butadiene-styrene rubber.
9. lithium rechargeable battery, this battery comprises battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in the battery container, the electrode group comprises reels or stacked positive plate, barrier film and negative plate successively, described positive plate contains conducting base and is coated in the positive electrode on this conducting base two sides, it is characterized in that described positive electrode is each described positive electrode among the claim 1-8.
CNA2006101723003A 2006-12-30 2006-12-30 Anode material of Li-ion secondary battery and battery containing the same Pending CN101212048A (en)

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Application publication date: 20080702