CN100583509C - Lithium secondary battery - Google Patents

Lithium secondary battery Download PDF

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CN100583509C
CN100583509C CN200610073006A CN200610073006A CN100583509C CN 100583509 C CN100583509 C CN 100583509C CN 200610073006 A CN200610073006 A CN 200610073006A CN 200610073006 A CN200610073006 A CN 200610073006A CN 100583509 C CN100583509 C CN 100583509C
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anode mixture
lithium
rechargeable battery
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mixture layer
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CN1848492A (en
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舆石真弓
东彪
松本和伸
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Maxell Ltd
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Hitachi Maxell Ltd
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Abstract

The present invention provides a lithium ion secondary battery having high capacity, high working voltage, and excellent load characteristics and excellent charge/discharge cycle characteristics when charges up at a high voltage. The lithium ion secondary battery has a positive electrode containing as an active material Li<SUB>p</SUB>Co<SUB>q</SUB>Ma<SUB>(1-q)</SUB>O<SUB>2</SUB>(A) and a compound (B) represented by general formula, Li<SUB>x</SUB>Ni<SUB>y</SUB>Co<SUB>z</SUB>Mb<SUB>(1-y-z)</SUB>O<SUB>2</SUB>, in a mass ratio of (B)/(A)=0.04 to 0.8, having a positive mix layer having a density of 3.7 g/cm<SP>3</SP>, wherein,0.5<=p<=1.2, 0<q<=1, 0.5<=x<=1.2, y+z<1, Y>0, z>0, Ma, Mb is at least one element selected from Al, Mn, Fe, Mg, Si, Ti, Zn, Mo, V, Sr, Sn, Sb, W, Ta, Nb, Ge, and Ba.

Description

Lithium rechargeable battery
Technical field
The present invention relates to lithium rechargeable battery, more particularly relate to the lithium rechargeable battery of high power capacity, high voltage and part throttle characteristics excellence.
Background technology
Lithium rechargeable battery is owing to have high voltage, a high-energy-density, presents the trend of increase as the demand of the driving power of portable machine etc. etc.Now, the positive active material of this lithium rechargeable battery mainly uses the cobalt acid lithium that capacity is big, invertibity is good.
Lithium rechargeable battery for present is accompanied by the improvement of the machine that is suitable for, and requires to have higher capacity.But for the battery that has used cobalt acid lithium, its battery capacity is basically near the limit.Therefore, about improving the capacity of lithium rechargeable battery, studying recently and substituting cobalt acid lithium, and using the theoretical discharge capacity lithium nickelate bigger, lithium nickel cobalt dioxide (for example specially permit No. 2511667 communique, No. 2699176 communiques of special permission, specially permit No. 3049727 communique) than the sour lithium of cobalt.In addition, also proposed will be by the part cobalt in other element substitution cobalts acid lithiums, part of nickel in the lithium nickelate and the compound that forms as the battery of active material (for example specially permit No. 3244314 communique, No. 3469836 communiques of special permission).
Summary of the invention
By using above-mentioned positive active material, can realize the high capacity of lithium rechargeable battery, but, also exist than the relatively poor aspect of battery of using cobalt acid lithium for the battery that has used above-mentioned each compound, still leave some room for improvement in these areas.
Use the battery of lithium nickelate to compare with the battery that uses cobalt acid lithium, the capacity that is caused by repeated charge reduces big, and operating voltage is low, and then capacity reduces big when discharging and recharging at a high speed.In addition,, compare with the battery that uses cobalt acid lithium for the battery that uses lithium nickel cobalt dioxide, relatively poor aspect operating voltage or the reduction of high speed charge-discharge characteristic.And then, for will be by the part cobalt in other element substitution cobalts acid lithiums, part of nickel in the lithium nickelate and the compound that forms as the battery of active material, compare with the battery that uses cobalt acid lithium, can not avoid the reduction of operating voltage.
The present invention finishes in view of the above problems, and its purpose is to provide the lithium rechargeable battery of high power capacity, operating voltage height, part throttle characteristics excellence.
Can realize being characterized as of lithium rechargeable battery of the present invention of above-mentioned purpose, its just having with (B)/(A) be 0.04～0.8 mass ratio contain compound (A) and (B) and density more than or equal to 3.7g/cm 3The anode mixture layer, described compound (A) is by general expression Li pCo qMa (1-q)O 2Expression, wherein, 0.5≤p≤1.2,0＜q≤1, at least a element of Ma for from Al, Mn, Fe, Mg, Si, Ti, Zn, Mo, V, Sr, Sn, Sb, W, Ta, Nb, Ge and Ba, selecting; Described compound (B) is by general expression Li xNi yCo zMb (1-y-z)O 2Expression, wherein, 0.5≤x≤1.2, y+z＜1, y＞0, z＞0, at least a element of Mb for from Al, Mn, Fe, Mg, Si, Ti, Zn, Mo, V, Sr, Sn, Sb, W, Ta, Nb, Ge and Ba, selecting.
Promptly, among the present invention, with special ratios and be used as the cobalt acid lithium based compound (A) of the ad hoc structure of representing by above-mentioned general expression of positive active material and the lithium nickel cobalt dioxide based compound (B) of the ad hoc structure represented by above-mentioned general expression, improve the density of the anode mixture layer that contains these active materials simultaneously, thereby realize using separately the unapproachable high capacity of cobalt acid lithium, in addition, the reduction of the operating voltage that is produced in the time of can suppressing to use the lithium nickel cobalt dioxide based compound separately, and then can realize the raising of high load characteristics and the raising of the charge under the high-voltage charge condition.
In lithium rechargeable battery of the present invention, above-mentioned anode mixture layer preferably contains the material with carbon element of 0.5～1.8 quality % as the electrical conductivity auxiliary agent.Thus, when realizing the lithium rechargeable battery high power capacity, can further improve part throttle characteristics.
In addition, lithium rechargeable battery of the present invention is preferably following battery: have nonaqueous electrolytic solution, described nonaqueous electrolytic solution contains the compound of contain fluorine atoms.Owing to adopt such structure, can further improve the part throttle characteristics of lithium rechargeable battery.
Above-mentioned positive active material and above-mentioned electrical conductivity auxiliary agent are the particle shape, for lithium rechargeable battery of the present invention, in above-mentioned anode mixture layer, preferably in the total amount of above-mentioned active material and electrical conductivity auxiliary agent, particle diameter is smaller or equal to 5 volume % smaller or equal to the ratio of the particle of 2 μ m.
Lithium rechargeable battery of the present invention, even for example charge under the high voltage more than or equal to 4.3V, invertibity is also excellent, can bring into play the favorable charge-discharge cycle characteristics.
According to the present invention, can provide the lithium rechargeable battery of high power capacity, high working voltage, part throttle characteristics excellence.
And then lithium rechargeable battery of the present invention also goes for implementing the purposes more than or equal to the high-voltage charge of 4.3V.
Description of drawings
Fig. 1 is the schematic diagram of an example of lithium rechargeable battery involved in the present invention, (a) is its vertical view, (b) is its part longitudinal section.
Fig. 2 is the oblique view of lithium rechargeable battery shown in Figure 1.
Symbol description
1 positive pole
2 negative poles
3 barrier films
4 battery cases
5 insulators
6 electrode laminates
7 anodal wiring bodies
8 negative pole wiring bodies
9 seal and use cover plate
10 insulated enclosure pads
11 terminals
12 insulators
13 terminal blocks
14 electrolyte inlets
15 safety valves
Embodiment
Lithium rechargeable battery of the present invention for example has following positive pole: by on the one side or two sides of the tabular conductive base of bringing into play the collector body function, formation contains the anode mixture layer of positive active material, electrical conductivity auxiliary agent and adhesive etc. and constitutes.
Above-mentioned anode mixture layer contains following active material: the compound that the part cobalt in the cobalt acid lithium is replaced by element M a, and promptly by general expression Li pCo qMa (1-q)O 2The compound (A) of (wherein, 0.5≤p≤1.2,0＜q≤1) expression; And the part cobalt in the lithium nickel cobalt dioxide or the part of nickel compound of being replaced by element M b, promptly by general expression Li xNi yCo zMb (1-y-z)O 2The compound (B) of (wherein, 0.5≤x≤1.2, y+z＜1, y＞0, z＞0) expression.
In the above-mentioned cobalt acid lithium based compound (A), after battery making just, be 0.95～1.2 as the p value of the addition of lithium.Lithium ion moves to negative pole during charging, and the p value can reduce gradually.But, if the p value less than 0.5, then the crystalline texture of positive active material can be collapsed, lithium ion is difficult to return to lattice structure during discharge, charge will reduce, therefore preferred p value is 0.5～1.2.
In the above-mentioned general expression of expression lithium nickel cobalt dioxide based compound (B), if the content y of Ni is too small, the effect that then improves battery capacity can diminish; If excessive, then the part throttle characteristics of battery tends to reduce.Therefore, the content y of Ni is preferably more than and equals 0.7 less than 0.9.In addition, if the content z of Co is excessive, the effect that then improves battery capacity can diminish; If too small, then the part throttle characteristics of battery tends to reduce.Therefore, the content z of Co is preferably more than and equals 0.1 less than 0.3.And then the content 1-y-z of substitutional element M is preferably 0.01～0.1.
For above-mentioned cobalt acid lithium based compound (A), at least a element of substitutional element Ma for from Al, Mn, Fe, Mg, Si, Ti, Zn, Mo, V, Sr, Sn, Sb, W, Ta, Nb, Ge and Ba, selecting.At least a element among the preferred Al of substitutional element Ma, Mn, Fe, Si, Ti, Zn or the Ba.
For above-mentioned lithium nickel cobalt dioxide based compound (B), at least a element of substitutional element Mb for from Al, Mn, Fe, Mg, Si, Ti, Zn, Mo, V, Sr, Sn, Sb, W, Ta, Nb, Ge and Ba, selecting.At least a element among the preferred Al of substitutional element Mb, Mn, Fe, Mg, Si, Ti, Zn, Sn or the Ba.
In above-mentioned anode mixture layer, for the content ratio of cobalt acid lithium based compound (A) and lithium nickel cobalt dioxide based compound (B), be more than or equal to 0.04 with mass ratio, be preferably greater than and equal 0.06; Smaller or equal to 0.8, preferably smaller or equal to 0.45.(A) active material by containing aforementioned proportion in the anode mixture layer and (B) active material can suppress the decline of operating voltage, part throttle characteristics when improving capacity, thus the battery that can form high working voltage and have excellent part throttle characteristics.
That is, if the ratio of above-mentioned (B)/(A) is too small, the effect of the capacity that then almost can't be improved; If above-mentioned ratio is excessive, the effect of then improving the operating voltage reduction can diminish.And then (damage when for example charging for 4.3～4.6V) times is than the cobalt acid lithium (LiCoO that does not contain Ma at high voltage for cobalt acid lithium based compound (A), lithium nickel cobalt dioxide based compound (B) 2) little.Therefore, use above-claimed cpd (A) and (B) as the battery of positive active material, for example compare as the battery of positive active material with using cobalt acid lithium, discharge and recharge in the time of can being formed on charging above-mentioned high voltage under invertibity well, the battery of excellent charge.
Above-mentioned cobalt acid lithium based compound (A), lithium nickel cobalt dioxide based compound (B) can be by will being adjusted to the regulation ratio the mixture of the salt that contains each element (sulfate, nitrate etc.), oxide, hydroxide etc. under 500～1000 ℃ of temperature, burn till synthetic.This burns till also and can carry out at twice.
Above-mentioned anode mixture layer in the lithium rechargeable battery of the present invention, its density is more than or equal to 3.7g/cm 3, be preferably greater than and equal 3.75g/cm 3By forming the anode mixture layer of such density, can realize the high capacity of battery.But, if the density of anode mixture layer is excessive, then being difficult to by the non-aqueous solution electrolysis liquid wetting, part throttle characteristics can reduce, so its density is preferably smaller or equal to 4.1g/cm 3Here, the density of above-mentioned anode mixture layer is the value of measuring by the following method.What cut the regulation area is provided with the anode mixture layer and the positive pole that forms on the one side of conductive base or two sides, use minimum scale to take by weighing its weight as the electronic balance of 1mg, from this weight, deduct the weight of conductive base, thereby calculate the weight of anode mixture layer.On the other hand, using minimum scale is the gross thickness of the above-mentioned positive pole in miking 10 places of 1 μ m, from the mean value of the value of deduction conductive base thickness and the volume that planimeter is calculated the anode mixture layer.Subsequently, with the above-mentioned weight of anode mixture layer above-mentioned volume, thereby obtain the density of anode mixture layer divided by the anode mixture layer.
For the density that makes the anode mixture layer reaches above-mentioned value, for example can adopt following method: use the top load forcing press, under the condition of its pressure of change, pressurization number of times, roll temperature, the anode mixture layer is carried out pressurized treatments.
Except above-mentioned active material, above-mentioned anode mixture layer also contains the electrical conductivity auxiliary agent.Among the present invention, the electrical conductivity auxiliary agent that is contained in the anode mixture layer, material with carbon elements such as preference such as carbon black, acetylene black, section's qin carbon black, graphite, carbon fiber.In the above-mentioned material with carbon element, from the viewpoint that the effect and the anode mixture layer of addition and conductivity contains the manufacturing of composition (aftermentioned), preferred acetylene black or section's qin carbon black.In addition, as the content of the material with carbon element of the electrical conductivity auxiliary agent in the anode mixture layer, for example be more than or equal to 0.5 quality %, be preferably more than and equal 0.8 quality %; Smaller or equal to 1.8 quality %, preferably smaller or equal to 1.5 quality %.For anode mixture layer related among the present invention, even reduce the electrical conductivity amount of auxiliary like this, also can guarantee the good electron conductibility, therefore when obtaining high power capacity, can further improve part throttle characteristics.
That is, for lithium rechargeable battery in the past, with cobalt acid lithium, LiMn2O4 (LiMn 2O 4) wait compound transition metal oxide to make anodal situation as active material, because the electronic conductivity of these compound transition metal oxides can not think big, therefore the above-mentioned illustrative material with carbon element that for example contains about 2～5 quality % in the anode mixture layer improves the electronic conductivity between positive active material as the electrical conductivity auxiliary agent.But, add the charge that adds that these electrical conductivity auxiliary agents can reduce active material in the anode mixture layer to the anode mixture layer, thereby become the key factor that hinders high capacity.In contrast,, can reduce the content in the anode mixture layer as mentioned above, therefore, can when realizing high capacity, further improve part throttle characteristics as the material with carbon element of electrical conductivity auxiliary agent for the present invention.Its reason is also indeterminate, but can infer, in the anode mixture layer, is above-mentioned formation and to make the anode mixture layer be the combination of above-specified high density by making active material, can realize that the content of electrical conductivity auxiliary agent reduces.
For above-mentioned active material and the electrical conductivity auxiliary agent of boning, also contain adhesive in the above-mentioned anode mixture layer.Can be suitable for Kynoar based polymer for example (containing polymer), rubber based polymer etc. as adhesive as the fluorochemical monomer group of the vinylidene of principal component monomer more than or equal to 80 quality %.Above-mentioned polymer also can be also with more than 2 kinds or 2 kinds.In addition, for adhesive, for example except pulverous adhesive, also can be to be dispersed in dispersion in the decentralized medium, to be dissolved in the form of the solution in the solvent and to supply with.
Fluorochemical monomer group as being used for synthetic above-mentioned Kynoar based polymer can enumerate: vinylidene; Vinylidene and other monomers mix mutually contains monomer mixture more than or equal to the vinylidene of 80 quality %.As above-mentioned other monomers, can enumerate PVF, trifluoro-ethylene, chlorotrifluoroethylene, tetrafluoroethene, hexafluoropropylene, fluoroalkyl vinyl ethers etc.
As above-mentioned rubber based polymer, can enumerate for example butadiene-styrene rubber (SBR), ethylene propylene diene rubber (EPDM), fluorubber etc.
The content of the adhesive in the anode mixture layer is more than or equal to 0.1 quality %, is preferably greater than to equal 0.3 quality %; Smaller or equal to 5 quality %, preferably smaller or equal to 2 quality %.If binder content is very few, the mechanical strength deficiency of anode mixture layer then, the anode mixture layer may be peeled off from conductive base.If binder content is too high, then the active matter quality in the anode mixture layer reduces, and battery capacity may reduce.
In addition, with the quantifier that closes of cobalt acid lithium based compound (A) and lithium nickel cobalt dioxide based compound (B), the content of the positive active material in the anode mixture layer is more than or equal to 93.2 quality %, is preferably greater than to equal 97.0 quality %; Smaller or equal to 99.4 quality %, preferably smaller or equal to 98.7 quality %.
Here, above-mentioned positive active material (cobalt acid lithium based compound (A), lithium nickel cobalt dioxide based compound (B)) and electrical conductivity auxiliary agent are the particle shape, in the total amount of above-mentioned active material and electrical conductivity auxiliary agent, particle diameter is preferably smaller or equal to 5 volume % smaller or equal to the ratio of the particle of 2 μ m, more preferably smaller or equal to 3 volume %.Like this, by the solution of above-mentioned active material, above-mentioned electrical conductivity auxiliary agent and above-mentioned adhesive or dispersion liquid and modulate contain anode mixture composition (slurry etc.) even long term storage, also can suppress generations such as aggegation, separation, sedimentation, be preferred aspect the manufacturing battery therefore.
The alleged positive active material or the particle diameter of electrical conductivity auxiliary agent are the following values of obtaining among the present invention: with positive pole impregnated in can the solvent of dissolved adhesive in, carry out ultrasonic Treatment, behind the separating particles (positive active material and electrical conductivity auxiliary agent), this particle of ormal weight is added in the water that has added surfactant, after disperseing by ultrasonic Treatment, utilize laser diffraction and scattering type particle size distribution device (Honeywell society makes " MICROTRAC ") to measure particle size distribution.
Positive pole with above-mentioned anode mixture layer for example can followingly be made: use above-mentioned active material, above-mentioned electrical conductivity auxiliary agent and disperse in solvent or the above-mentioned adhesive of dissolving and modulate and contain anode mixture composition (slurry etc.), on the one side of conductive base or two sides coating this contain the anode mixture composition, carry out drying again.The manufacture method of positive pole involved in the present invention is not limited to this, also can adopt additive method.As containing spendable solvent in the anode mixture composition, can enumerate for example N-N-methyl-2-2-pyrrolidone N-(NMP), water, toluene, dimethylbenzene etc.
As containing the method that the anode mixture composition is coated on the conductive base surface, can adopt is the known various coating processes of representative with extrusion coated device, reverse rollers, blade coating machine, glue spreader etc. for example.
As the conductive base of positive pole, can adopt and for example metallicity electric conducting materials such as aluminium, stainless steel, titanium are processed into net, perforated metal, foam metal, tabular paper tinsel etc.For example preferred 8～16 μ m of the thickness of conductive base.
The thickness of the anode mixture layer that forms on the conductive base surface in addition, for example is preferably 30～150 μ m in dried thickness.
In lithium ion battery of the present invention,, can enumerate material adsorbable, that emit lithium as employed negative electrode active material in becoming the negative pole to the utmost point of above-mentioned positive pole.Can enumerate material with carbon elements such as the carbonaceous material that for example has Turbostratic, native graphite, Delanium, vitreous carbon.These materials do not contain lithium when making negative pole, but do the time spent as negative electrode active material, can become the state that contains lithium by chemical method, electrochemical method etc.In addition, except above-mentioned material with carbon element, as can enumerating for example lithium metal or lithium-containing compound as adsorbable, the material of emitting lithium of negative electrode active material.As above-mentioned lithium-containing compound can illustration lithium alloy for example.As lithium alloy, can enumerate for example alloy of lithium such as lithium-aluminium, lithium-lead, lithium-bismuth, lithium-indium, lithium-gallium, lithium-indium-gallium and other metals.
Negative pole for example can followingly be made: add adhesive in above-mentioned negative electrode active material, add the electrical conductivity auxiliary agent as required, and then add solvent and modulate and contain cathode agent composition (slurry etc.), it is coated on the one side or two sides of conductive base, carry out drying, form anode mixture layer.Contain employed solvent in the cathode agent composition as above-mentioned, can enumerate for example water, NMP, toluene, dimethylbenzene etc.In addition, above-mentioned when containing the cathode agent composition in modulation, adhesive preferably uses the solution that dissolves in advance or the suspension-turbid liquid of dispersion in organic solvent or water, mixes mutually with solids such as above-mentioned negative electrode active material.In addition, with above-mentioned lithium metal or lithium alloy situation as negative electrode active material, can only constitute negative pole, also the anode mixture layer that only is made of this negative electrode active material can be pressed together on the one side of conductive base or the two sides and constitute negative pole by this negative electrode active material.
The adhesive that uses in the making as negative pole can be suitable for for example Kynoar based polymer, rubber based polymer, cellulose-based polymer etc.Above-mentioned polymer can be also with more than 2 kinds or 2 kinds.
As above-mentioned Kynoar based polymer and above-mentioned rubber based polymer, for example can use with top illustrated anode mixture layer with the same material of adhesive.In addition, as cellulose-based polymer, can enumerate for example carboxymethyl cellulose (CMC), methylcellulose, ethyl cellulose, hydroxypropyl cellulose, HEMC, hydroxypropyl methylcellulose etc.
In addition, as the electrical conductivity auxiliary agent that is contained in the anode mixture layer, can be suitable for for example flaky graphite, carbon black, section's qin carbon black, acetylene black, carbon fiber etc.
As the method that the cathode agent composition is coated on the conductive base, for example can enumerate in the above as the anode mixture composition being coated on method on the conductive base and illustrative known various coating processes.
As the conductive base of negative pole, can adopt and for example metallicity electric conducting materials such as aluminium, stainless steel, titanium, copper are processed into net, perforated metal, foam metal, tabular paper tinsel etc.For example preferred 5～12 μ m of the thickness of conductive base.
The thickness of formed anode mixture layer is in dried thickness on the conductive base surface, and for example the cobalt acid lithium based compound (A) when the anode mixture layer is the cobalt acid lithium (LiCoO that does not contain Ma 2) time, for example be preferably 40～160 μ m; When the cobalt of anode mixture layer acid lithium based compound (A) when containing Ma, for example be preferably 40～170 μ m.In addition, when anode mixture layer for example contained above-mentioned negative electrode active material and adhesive, the content of negative electrode active material for example was preferably 90～99.8 quality %.
In addition, when anode mixture layer for example contained above-mentioned negative electrode active material and adhesive, the content of adhesive for example was preferably 0.2～10 quality %, more preferably 0.5～2 quality %.If the content of adhesive is low excessively, the mechanical strength deficiency of anode mixture layer then, anode mixture layer may be peeled off from conductive base.In addition, if the too high levels of adhesive, then the active matter quality in the anode mixture layer reduces, and battery capacity may reduce.
And then when also containing the electrical conductivity auxiliary agent in anode mixture layer, the content of the electrical conductivity auxiliary agent in the anode mixture layer for example is preferably 0.1～1.0 quality %.
Lithium rechargeable battery of the present invention for example can followingly be made: clip barrier film and be rolled into helical form between positive pole of making as mentioned above and negative pole, thereby produce helix electrode body, again this electrode body is inserted in the battery case of aluminium, aluminium alloy, the iron of having implemented Nickel Plating Treatment or stainless steel etc., inject nonaqueous electrolytic solution, seal.In addition, in battery of the present invention, can discharge to outside batteries when usually the gas that produces at inside battery rises to stage of a certain level pressure power, quote and be used to prevent the battery known in the past explosion-proof mechanism of breaking under high pressure.
Barrier film as being clipped between positive pole and the negative pole is not particularly limited, and can be suitable for known in the past barrier film.The cobalt sour lithium (LiCoO of cobalt acid lithium based compound (A) when the anode mixture layer for not containing Ma 2) time, can be suitable for thickness for example is 30～70% microporosity polyethylene film or microporosity polypropylene film, polyethylene-polypropylene composite membrane etc. at 5～30 μ m, percent opening.When the cobalt of anode mixture layer acid lithium based compound (A) when containing Ma, can suitable thicknesses be 30～70% microporosity polyethylene film or microporosity polypropylene screen, polyethylene-polypropylene composite membrane etc. at 10～50 μ m, percent opening.
As nonaqueous electrolytic solution (hereinafter to be referred as electrolyte), use electrolyte dissolution such as lithium salts in organic solvent and the electrolyte that obtains.As this electrolyte, can enumerate for example by general expression LiXF nThe inorganic lithium salt of (in the formula, X is P, As, Sb or B, and n is 6 when X is P, As or Sb, and n was 4 when X was B) expression, fluorine-containing organolithium imide salts etc.These electrolyte can be distinguished use separately, also can be also with more than 2 kinds or 2 kinds.
Dissolve above-mentioned electrolytical organic solvent as being used to, be not particularly limited, for example can enumerate 1,2-dimethoxy-ethane, 1,2-diethoxyethane, dimethoxy propane, 1, ethers such as 3-dioxolanes, oxolane, 2-methyltetrahydrofuran; Ester classes such as propene carbonate, ethylene carbonate, gamma-butyrolacton, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate; Sulfur-containing compounds such as sulfolane; Fluoro linear carbonate (carbonic acid fluoroform ethyl ester etc.), fluoric cyclic carbonate (carbonic acid tetrafluoroethene ester etc.), fluoro chain ether (perfluorobutyl methyl ethers etc.) etc. contain fluorous solvent.These solvents can use separately, also can mix use more than 2 kinds or 2 kinds.In the above-mentioned organic solvent, even because ester class reactivity with positive active material under high voltage is also little, the effect that improves storage characteristics is obvious, thereby is preferred.The angle of the stability of electrolyte is considered when charging from improving, and this ester class is preferably greater than in all electrolyte solvents and equals 20 volume %.
As the above-mentioned electrolytical concentration in the electrolyte, when containing different electrolyte more than 2 kinds or 2 kinds, preferred all concentration is 0.4～1.6mol/l, more preferably 0.6～1.4mol/l.
In electrolyte, the preferred compound that contains fluorine atom that adds.Can further improve the part throttle characteristics of lithium rechargeable battery thus.As the compound that contains fluorine atom, can enumerate aromatic compound, fluoro linear carbonate, fluoric cyclic carbonate of contain fluorine atoms such as fluorobenzene etc.For example be preferably 0.5～7 quality % as the concentration of the compound that contains fluorine atom in electrolyte.
Lithium rechargeable battery of the present invention is because the charge under high power capacity, operating voltage height, part throttle characteristics and the high-voltage charge condition is also excellent, by bringing into play these characteristics, go for being accompanied by the purposes such as power supply of the big portable instrument of the power consumption of multifunction, automobile, bicycle, motorcycle etc.
Embodiment
Below based on embodiment the present invention is described in detail.But the present invention is not limited to following embodiment, and the change of being carried out in the scope of described intention before and after not breaking away from is included in the technical scope of the present invention.
Embodiment 1
＜anodal making 〉
For active material, using mass ratio with (B)/(A) is that 0.25 to mix as the average grain diameter of cobalt acid lithium based compound (A) be the sour lithium LiCoO of cobalt of 13 μ m 2With the average grain diameter as lithium nickel cobalt dioxide based compound thing (B) be the LiNi of 12 μ m 0.81Co 0.16Al 0.03O 2Resulting mixture.Modulation contains this active material admixture of 98 mass parts, 1 mass parts as the acetylene black of electrical conductivity auxiliary agent and the 1 mass parts Kynoar as adhesive, and then contains and contain the anode mixture composition as the NMP of solvent.Following the carrying out of modulation that contains the anode mixture composition: Kynoar is dissolved among the NMP in advance, in this solution, adds above-mentioned active material admixture and acetylene black, further add NMP, when fully disperseing, regulate viscosity while stir.Be that the two sides of the aluminium foil of 15 μ m uses glue spreader evenly to be coated with this to contain the anode mixture composition at thickness, utilize roll squeezer to roll processing subsequently, thus obtain having on the two sides of conductive base the anode mixture layer, all thickness is the sheet positive pole of 130 μ m.The density of the anode mixture layer of the positive pole of Zhi Zuoing is 3.85g/cm like this 3
The making of＜negative pole 〉
Use specific area to be 3.6m for active material 2The graphite of/g.In addition, use the CMC aqueous solution of SBR suspension-turbid liquid and concentration 1.5 quality % for adhesive.Prepare the SBR suspension-turbid liquid and the CMC aqueous solution, making solid constituent separately is 1 mass parts (being that the adhesive solids composition all is 2 mass parts), mixes mutually with the above-mentioned active material of 98 mass parts and modulates and contain the cathode agent composition.At thickness is the two sides of the Copper Foil of 8 μ m, use glue spreader evenly to be coated with this and contain the cathode agent composition, utilize roll squeezer to roll processing subsequently, thus obtain having on the two sides of conductive base anode mixture layer, all thickness is the sheet negative pole of 125 μ m.The density of the anode mixture layer of the negative pole of Zhi Zuoing is 1.75g/cm thus 3
The assembling of＜battery 〉
The wiring body is installed on above-mentioned positive pole and negative pole, and making anodal and negative pole accompany by thickness is the barrier film that constitutes of the microporosity polyethylene-polypropylene composite membrane of 14 μ m and overlapping, pressurizes after being rolled into helical form, thereby obtains the electrode laminate of flat winding-structure.After this electrode laminate twined insulating tape, insert external dimensions and be in the battery case of square (square tube shape) of high 50mm * wide 34mm * thick 4mm, carry out the welding of wiring body and seal with the laser welding of cover plate to the open end of battery case.Then, inject electrolyte from being arranged on the electrolyte inlet that seals with on the cover plate in battery case, after electrolyte fully soaked into barrier film etc., sealing electrolyte inlet formed air-tight state.Here, use the following material that obtains for electrolyte: the concentration with 1.0mol/l in 1: 2 (volume ratio) mixed solvent of ethylene carbonate and methyl ethyl carbonate is dissolved LiPF 6, add the fluorobenzene of 3 quality % again.Subsequently, carry out precharge and aging (aging), thus the square lithium ion secondary battery that obtains having structure shown in Figure 1, outward appearance shown in Figure 2.
At this battery illustrated in figures 1 and 2 is described, positive pole 1 and negative pole 2 clip barrier film 3 and are rolled into after the helical form as mentioned above, pressurization forms flat, obtains the electrode laminate 6 of flat winding-structure, and itself and above-mentioned electrolyte are contained in the square battery case 4 simultaneously.Here, in Fig. 1, for fear of complicated, as make anodal 1 or during negative pole 2 metal forming, electrolyte etc. of employed conductive base illustrate.
Battery case 4 is to be made by aluminium alloy, constitutes the housing material of battery, these battery case 4 double as positive terminals.And, be provided with the insulator 5 that constitutes by polythene strip in the bottom of battery case 4, draw from the electrode laminate 6 of the flat winding-structure that constitutes by above-mentioned anodal 1, negative pole 2 and barrier film 3 and be connected anodal 1 and the anodal wiring body 7 and the negative pole wiring body 8 of an end of negative pole 2 respectively.In addition, the aluminium alloy system of the peristome of closing battery box 4 seal with cover plate 9 on through the insulated enclosure pad 10 of polypropylene system the terminal 11 of stainless steel is set, the terminal block 13 of stainless steel is set through insulator 12 on this terminal 11.
And this cover plate 9 is inserted into the peristome of above-mentioned battery case 4, and by welding both junction surfaces, the peristome of battery case 4 is closed, thereby inside battery is sealed.
On cover plate 9, be provided with electrolyte inlet 14, when assembled battery, in battery external packing body, inject electrolyte from this electrolyte inlet 14, subsequently, sealing electrolyte inlet 14.Therefore, though in Fig. 1, express electrolyte inlet 14, in the battery of finishing, the 14th, the vestige of the electrolyte inlet of sealing.In addition, cover plate 9 is provided with the safety valve 15 of explosion-proof usefulness.
For the battery of this embodiment 1, by anodal wiring body 7 being welded direct on the cover plate 9 function of electrode box 4 and cover plate 9 performance positive terminals; By negative pole wiring body 8 is welded on the terminal block 13, with negative pole wiring body 8 and terminal 11 conductings, the function of terminal 11 performance negative terminals, but according to the material of electrode box 4 etc. positive and negatively sometimes also can reverse through this terminal block 13.
Fig. 2 is the oblique view of the outward appearance of the above-mentioned battery shown in Figure 1 of pattern ground expression, and the illustrated content of this Fig. 2 is that the above-mentioned battery of expression is the situation of rectangular cell, has represented battery among this Fig. 2 briefly, has only shown certain components in the battery structure parts among the figure.In addition, in Fig. 1, the part of interior all sides of electrode body is not made the cross section.
Embodiment 2
When modulation contains the anode mixture composition, the content of cobalt acid lithium based compound (A) and lithium nickel cobalt dioxide based compound (B) is changed to 0.05 than (B)/(A) (mass ratio), in addition, make lithium rechargeable battery similarly to Example 1.
Embodiment 3
When modulation contains the anode mixture composition, the content of cobalt acid lithium based compound (A) and lithium nickel cobalt dioxide based compound (B) is changed to 0.67 than (B)/(A) (mass ratio), in addition, make lithium rechargeable battery similarly to Example 1.
Embodiment 4
Coating weight when the two sided coatings that is adjusted at aluminium foil contains the anode mixture composition and the condition of utilizing the calendering of roll squeezer to handle make the density of anode mixture layer change to 3.76g/cm 3, in addition, make lithium rechargeable battery similarly to Example 1.
Embodiment 5
Coating weight when the two sided coatings that is adjusted at aluminium foil contains the anode mixture composition and the condition of utilizing the calendering of roll squeezer to handle make the density of anode mixture layer change to 3.71g/cm 3, in addition, make lithium rechargeable battery similarly to Example 1.
Embodiment 6
Composition for the solid constituent that contains the anode mixture composition, the mixture of change cobalt acid lithium based compound (A) and lithium nickel cobalt dioxide based compound (B) is that 97 mass parts, acetylene black are that 2 mass parts, Kynoar are 1 mass parts, in addition, make lithium rechargeable battery similarly to Example 1.
Embodiment 7
Electrolyte is changed in 1: 2 (volume ratio) mixed solvent of ethylene carbonate and methyl ethyl carbonate concentration dissolving LiPF with 1.0mol/l 6Resulting solution in addition, is made lithium rechargeable battery similarly to Example 1.
Embodiment 8
Lithium nickel cobalt dioxide based compound (B) is changed to the LiNi of average grain diameter 12 μ m 0.81Co 0.16Mn 0.03O 2, in addition, make lithium rechargeable battery similarly to Example 1.
Embodiment 9
Composition for the solid constituent that contains the anode mixture composition, the mixture of change cobalt acid lithium based compound (A) and lithium nickel cobalt dioxide based compound (B) is that 98.6 mass parts, acetylene black are that 0.4 mass parts, Kynoar are 1 mass parts, in addition, make lithium rechargeable battery similarly to Example 1.
Embodiment 10
Lithium nickel cobalt dioxide based compound (B) is changed to the LiNi of average grain diameter 10 μ m 0.81Co 0.16Mg 0.03O 2, in addition, make lithium rechargeable battery similarly to Example 1.
Embodiment 11
Lithium nickel cobalt dioxide based compound (B) is changed to the LiNi of average grain diameter 9 μ m 0.81Co 0.16Si 0.03O 2, in addition, make lithium rechargeable battery similarly to Example 1.
Embodiment 12
Lithium nickel cobalt dioxide based compound (B) is changed to the LiNi of average grain diameter 11 μ m 0.81Co 0.16Ti 0.03O 2, in addition, make lithium rechargeable battery similarly to Example 1.
Embodiment 13
Lithium nickel cobalt dioxide based compound (B) is changed to the LiNi of average grain diameter 8 μ m 0.81Co 0.16Zn 0.03O 2, in addition, make lithium rechargeable battery similarly to Example 1.
Embodiment 14
Lithium nickel cobalt dioxide based compound (B) is changed to the LiNi of average grain diameter 12 μ m 0.81Co 0.16Sn 0.03O 2, in addition, make lithium rechargeable battery similarly to Example 1.
Embodiment 15
Lithium nickel cobalt dioxide based compound (B) is changed to the LiNi of average grain diameter 10 μ m 0.81Co 0.16Ba 0.03O 2, in addition, make lithium rechargeable battery similarly to Example 1.
Embodiment 16
＜anodal making 〉
For active material, using the mass ratio with (B)/(A) is that 0.25 average grain diameter of mixing as cobalt acid lithium based compound (A) is the LiCo of 13 μ m 0.97Mg 0.03O 2With the average grain diameter as lithium nickel cobalt dioxide based compound thing (B) be the LiNi of 12 μ m 0.81Co 0.16Al 0.03O 2Resulting mixture.Modulation contains this active material admixture of 98 mass parts, 1 mass parts as the acetylene black of electrical conductivity auxiliary agent and the 1 mass parts Kynoar as adhesive, and then contains and contain the anode mixture composition as the NMP of solvent.Following the carrying out of modulation that contains the anode mixture composition: Kynoar is dissolved among the NMP in advance, in this solution, adds above-mentioned active material admixture and acetylene black, further add NMP, when fully disperseing, regulate viscosity while stir.Be that the two sides of the aluminium foil of 15 μ m uses glue spreader evenly to be coated with this to contain the anode mixture composition at thickness, utilize roll squeezer to roll processing subsequently, thus obtain having on the two sides of conductive base the anode mixture layer, all thickness is the sheet positive pole of 130 μ m.The density of the anode mixture layer of the positive pole of Zhi Zuoing is 3.85g/cm like this 3Except the positive pole that uses such making, make lithium rechargeable battery similarly to Example 1.
Embodiment 17
When modulation contains the anode mixture composition, the content of cobalt acid lithium based compound (A) and lithium nickel cobalt dioxide based compound (B) is changed to 0.05 than (B)/(A) (mass ratio), in addition, make lithium rechargeable battery similarly to Example 16.
Embodiment 18
When modulation contains the anode mixture composition, the content of cobalt acid lithium based compound (A) and lithium nickel cobalt dioxide based compound (B) is changed to 0.67 than (B)/(A) (mass ratio), in addition, make lithium rechargeable battery similarly to Example 16.
Embodiment 19
Coating weight when the two sided coatings that is adjusted at aluminium foil contains the anode mixture composition and the condition of utilizing the calendering of roll squeezer to handle make the density of anode mixture layer change to 3.76g/cm 3, in addition, make lithium rechargeable battery similarly to Example 16.
Embodiment 20
Coating weight when the two sided coatings that is adjusted at aluminium foil contains the anode mixture composition and the condition of utilizing the calendering of roll squeezer to handle make the density of anode mixture layer change to 3.71g/cm 3, in addition, make lithium rechargeable battery similarly to Example 16.
Embodiment 21
Composition for the solid constituent that contains the anode mixture composition, the mixture of change cobalt acid lithium based compound (A) and lithium nickel cobalt dioxide based compound (B) is that 97 mass parts, acetylene black are 2 mass parts, Kynoar 1 mass parts, in addition, make lithium rechargeable battery similarly to Example 16.
Embodiment 22
Electrolyte is changed in 1: 2 (volume ratio) mixed solvent of ethylene carbonate and methyl ethyl carbonate the resulting solution of concentration dissolving LiPF6 with 1.0mol/l, in addition, make lithium rechargeable battery similarly to Example 16.
Embodiment 23
Cobalt acid lithium based compound (A) is changed to the LiCo of average grain diameter 14 μ m 0.96Ti 0.04O 2, in addition, make lithium rechargeable battery similarly to Example 16.
Embodiment 24
Cobalt acid lithium based compound (A) is changed to the LiCo of average grain diameter 13 μ m 0.97Sn 0.03O 2, in addition, make lithium rechargeable battery similarly to Example 16.
Embodiment 25
Cobalt acid lithium based compound (A) is changed to the LiCo of average grain diameter 10 μ m 0.97Si 0.03O 2, in addition, make lithium rechargeable battery similarly to Example 16.
Embodiment 26
Cobalt acid lithium based compound (A) is changed to the LiCo of average grain diameter 9 μ m 0.96Al 0.04O 2, in addition, make lithium rechargeable battery similarly to Example 16.
Embodiment 27
Lithium nickel cobalt dioxide based compound (B) is changed to the LiNi of average grain diameter 12 μ m 0.81Co 0.16Mn 0.03O 2, in addition, make lithium rechargeable battery similarly to Example 16.
Embodiment 28
Lithium nickel cobalt dioxide based compound (B) is changed to the LiNi of average grain diameter 11 μ m 0.81Co 0.16Mg 0.03O 2, in addition, make lithium rechargeable battery similarly to Example 16.
Embodiment 29
Lithium nickel cobalt dioxide based compound (B) is changed to the LiNi of average grain diameter 12 μ m 0.81Co 0.16Si 0.03O 2, in addition, make lithium rechargeable battery similarly to Example 16.
Embodiment 30
Lithium nickel cobalt dioxide based compound (B) is changed to the LiNi of average grain diameter 9 μ m 0.81Co 0.16Ti 0.03O 2, in addition, make lithium rechargeable battery similarly to Example 16.
Embodiment 31
Lithium nickel cobalt dioxide based compound (B) is changed to the LiNi of average grain diameter 8 μ m 0.81Co 0.16Zn 0.03O 2, in addition, make lithium rechargeable battery similarly to Example 16.
Embodiment 32
Lithium nickel cobalt dioxide based compound (B) is changed to the LiNi of average grain diameter 10 μ m 0.81Co 0.16Sn 0.03O 2, in addition, make lithium rechargeable battery similarly to Example 16.
Embodiment 33
Lithium nickel cobalt dioxide based compound (B) is changed to the LiNi of average grain diameter 8 μ m 0.81Co 0.16Ba 0.03O 2, in addition, make lithium rechargeable battery similarly to Example 16.
Embodiment 34
Composition for the solid constituent that contains the anode mixture composition, the mixture of change cobalt acid lithium based compound (A) and lithium nickel cobalt dioxide based compound (B) is that 98.6 mass parts, acetylene black are that 0.4 mass parts, Kynoar are 1 mass parts, in addition, make lithium rechargeable battery similarly to Example 16.
Comparative example 1
When modulation contains the anode mixture composition, the content of cobalt acid lithium based compound (A) and lithium nickel cobalt dioxide based compound (B) is changed to 0.03 than (B)/(A) (mass ratio), in addition, make lithium rechargeable battery similarly to Example 1.
Comparative example 2
When modulation contains the anode mixture composition, the content of cobalt acid lithium based compound (A) and lithium nickel cobalt dioxide based compound (B) is changed to 0.9 than (B)/(A) (mass ratio), in addition, make lithium rechargeable battery similarly to Example 1.
Comparative example 3
Coating weight when the two sided coatings that is adjusted at aluminium foil contains the anode mixture composition and the condition of utilizing the calendering of roll squeezer to handle make the density of anode mixture layer change to 3.67g/cm 3, in addition, make lithium rechargeable battery similarly to Example 1.
Comparative example 4
Lithium nickel cobalt dioxide based compound (B) is changed to the LiNi of average grain diameter 12 μ m 0.8Co 0.2O 2, in addition, make lithium rechargeable battery similarly to Example 1.
Comparative example 5
When modulation contains the anode mixture composition, the content of cobalt acid lithium based compound (A) and lithium nickel cobalt dioxide based compound (B) is changed to 0.03 than (B)/(A) (mass ratio), in addition, make lithium rechargeable battery similarly to Example 16.
Comparative example 6
When modulation contains the anode mixture composition, the content of cobalt acid lithium based compound (A) and lithium nickel cobalt dioxide based compound (B) is changed to 0.9 than (B)/(A) (mass ratio), in addition, make lithium rechargeable battery similarly to Example 16.
Comparative example 7
Coating weight when the two sided coatings that is adjusted at aluminium foil contains the anode mixture composition and the condition of utilizing the calendering of roll squeezer to handle make the density of anode mixture layer change to 3.67g/cm 3, in addition, make lithium rechargeable battery similarly to Example 16.
Comparative example 8
When modulation contains the anode mixture composition, as active material, do not use the mixture of cobalt acid lithium based compound (A) and lithium nickel cobalt dioxide based compound (B), and only use cobalt acid lithium based compound (A), except not using lithium nickel cobalt dioxide based compound (B), make lithium rechargeable battery similarly to Example 16.
For the embodiment 1～34 that makes as mentioned above and the battery of comparative example 1～8, carry out following battery behavior evaluation.
The mensuration of＜capacity and operating voltage 〉
At first, when representing charging and discharging currents, suppose that 950mA is 1C, the current limit circuit of 1C is set, carry out initial charge, be discharged to 3.0V with 1C then with the constant voltage of 4.2V with C.Suppose that this discharges and recharges is 1 circulation, the charging and discharging currents with 1C carries out discharging and recharging of the 2nd circulation equally, the voltage when 50% of discharge capacity at this moment and this capacity of obtaining discharges.
＜part throttle characteristics evaluation 〉
For the battery of embodiment 1～34 and comparative example 1～8, with above-mentioned same condition repeated charge, be discharged to 3.0V at the 3rd circulation time with 0.2C, with the charging of above-mentioned same condition after, discharge with 2C at the 4th circulation time.The discharge capacity of the 2C of the 4th circulation of this moment multiply by 100 again divided by the discharge capacity of the 0.2C of the 3rd circulation, estimates as part throttle characteristics (%) with the result who obtains.
＜charge evaluation 〉
Battery for embodiment 16～34 and comparative example 5～8, to carry out discharging and recharging of 500 circulations with above-mentioned same condition, the discharge capacity of the 500th circulation multiply by 100 again divided by the discharge capacity of the 1st circulation, and the result who obtains estimates as charge (%).
Charge under the＜high-voltage charge condition 〉
For the battery of embodiment 16～34 and comparative example 5～8, when representing charging and discharging currents, suppose that 950mA is 1C with C, the current limit circuit of 1C is set, carry out initial charge with the constant voltage of 4.4V, be discharged to 3.0V with 1C subsequently.Suppose that discharging and recharging under this condition is 1 circulation, obtain the 100th discharge capacity that discharges and recharges, it is divided by the discharge capacity of the 1st circulation, multiply by 100 again, the result who obtains estimates as the charge under the high-voltage charge condition (%) (hereinafter referred to as " high voltage charge ").
For the battery of embodiment 1～34 and comparative example 1～8, the anode mixture layer density of each battery and the evaluation result of various battery behaviors are shown in Table 1 in the lump.Here, (B)/(A) in the table 1 is that the content of cobalt acid lithium based compound (A) in the anode mixture layer and lithium nickel cobalt dioxide based compound (B) is than (mass ratio).
By table 1 and table 2 as can be known, the lithium rechargeable battery of embodiments of the invention 1～34, capacity height and part throttle characteristics excellence, in addition, as shown in Table 2, the lithium rechargeable battery of embodiment 16～34 has excellent charging and discharging cycle characteristic and high voltage charge.
Table 1
Table 2
(B)/(A) Density (g/cm 3) Capacity (mAh) Voltage (V) during 50% discharge Part throttle characteristics (%) Charge (%) High pressure charge (%)
Embodiment 16 0.25 3.85 986 3.76 98.6 86 65
Embodiment 17 0.05 3.94 971 3.78 98.2 87 67
Embodiment 18 0.67 3.78 992 3.75 97.7 85 62
Embodiment 19 0.25 3.76 984 3.74 97.2 86 64
Embodiment 20 0.25 3.71 982 3.73 96.9 85 61
Embodiment 21 0.25 3.81 987 3.79 98.8 87 65
Embodiment 22 0.25 3.85 982 3.73 97.3 85 63
Embodiment 23 0.25 3.82 980 3.74 97.8 86 66
Embodiment 24 0.25 3.84 981 3.75 98.2 86 66
Embodiment 25 0.25 3.84 980 3.73 97.9 86 65
Embodiment 26 0.25 3.85 982 3.75 98.3 86 66
Embodiment 27 0.25 3.82 980 3.79 97.9 84 63
Embodiment 28 0.25 3.85 984 3.78 98.5 87 66
Embodiment 29 0.25 3.82 981 3.75 98.0 86 65
Embodiment 30 0.25 3.83 978 3.73 97.8 86 65
Embodiment 31 0.25 3.83 980 3.75 98.2 85 64
Embodiment 32 0.25 3.82 985 3.74 98.7 86 65
Embodiment 33 0.25 3.85 977 3.73 97.9 85 65
Embodiment 34 0.25 3.92 981 3.73 97.2 83 61
Comparative example 5 0.03 3.98 955 3.79 98.3 86 62
Comparative example 6 0.9 3.71 994 3.58 94.3 82 58
Comparative example 7 0.25 3.67 973 3.66 93.2 79 57
Comparative example 8 0 3.98 940 3.72 98.2 86 60

Claims (4)

1. lithium rechargeable battery is characterized in that:
It is just having density more than or equal to 3.7g/cm 3The anode mixture layer;
Contain compd A and compd B as active material with the mass ratio of B/A=0.04～0.8 in the described anode mixture layer;
Described compd A is by general expression Li pCo qMa (1-q)O 2Expression, wherein, 0.5≤p≤1.2,0＜q＜1, at least a element of Ma for from Al, Mn, Fe, Mg, Si, Ti, Zn, Mo, V, Sr, Sn, Sb, W, Ta, Nb, Ge and Ba, selecting;
Described compd B is by general expression Li xNi yCo zMb (1-y-z)O 2Expression, wherein, 0.5≤x≤1.2, y+z＜1, y＞0, z＞0, at least a element of Mb for from Al, Mn, Fe, Mg, Si, Ti, Zn, Mo, V, Sr, Sn, Sb, W, Ta, Nb, Ge and Ba, selecting;
And described anode mixture layer contains the material with carbon element of 0.5～1.8 quality % as the electrical conductivity auxiliary agent.
2. lithium rechargeable battery according to claim 1 is characterized in that: have nonaqueous electrolytic solution, described nonaqueous electrolytic solution contains the compound of contain fluorine atoms.
3. lithium rechargeable battery according to claim 1, it is characterized in that: described active material that contains in the described anode mixture layer and described electrical conductivity auxiliary agent are the particle shape, in the total amount of this active material and this electrical conductivity auxiliary agent, the particle diameter of being measured by the laser diffraction and scattering method is smaller or equal to 5 volume % smaller or equal to the ratio of the particle of 2 μ m.
4. lithium rechargeable battery according to claim 1 is characterized in that: charge with the voltage more than or equal to 4.3V.
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