CN100350650C - Nonaqueous electrolyte secondary cell - Google Patents

Nonaqueous electrolyte secondary cell Download PDF

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CN100350650C
CN100350650C CNB038221144A CN03822114A CN100350650C CN 100350650 C CN100350650 C CN 100350650C CN B038221144 A CNB038221144 A CN B038221144A CN 03822114 A CN03822114 A CN 03822114A CN 100350650 C CN100350650 C CN 100350650C
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particle
mentioned
active material
nonaqueous electrolytic
electrolytic battery
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CN1682391A (en
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加纳幸司
藤原雅史
吉田秀纪
志子田将贵
竹内肇
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Toshiba Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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

Abstract

A nonaqueous electrolyte secondary cell which has a positive electrode containing a positive electrode active material, a negative electrode and a nonaqueous electrolyte, wherein the positive electrode active material comprises oxide particles represented by the following formula (A) and oxide particles represented by the following formula (B), the above oxide particles represented by the following formula (A) account for more than 50 wt % of the above positive electrode active material, and the above positive electrode active material satisfies the following formulae (1) to (5), LixNiyCozMwO2 (A) LiaCobMcO2 (B) 1.4<= (DN90/DN50)<= 2 (1) 1.4 <= (DN50/DN10) <= 2 (2) 1.4 <= (DC90/DC50) <= 2 (3) 1.4<= (DC50/DC10)<= 2 (4) 1.5<= (DN50/DC50)<= 2.5 (5).

Description

Rechargeable nonaqueous electrolytic battery
Technical field
The present invention relates to rechargeable nonaqueous electrolytic battery.
Background technology
In recent years, along with the miniaturization and the lightweight of electronic instruments such as VTR, mobile phone, laptop computer, people expectation can improve these instruments power supply, be the energy density of secondary cell.Be opportunity thus,, will adopt LiCoO at present being that the research of the rechargeable nonaqueous electrolytic battery of negative pole vigorously launches with the lithium 2Lithium rechargeable battery practicability for positive active material.
And as the negative pole of rechargeable nonaqueous electrolytic battery, use lithium, lithium alloy or inhale the compound that storage discharges lithium.In addition, as nonaqueous electrolyte, adopt is dissolved in lithium salts (electrolyte) in the nonaqueous solvents and the material that forms more.As relevant nonaqueous solvents, known have propylene carbonate (PC), carbonic acid ethylidene ester (EC), ethylmethyl carbonate (EMC), dimethyl carbonate (DMC), a carbonic acid diethyl ester (DEC), 1,2-dimethoxy-ethane (DME), gamma-butyrolacton (γ-BL), oxolane (THF), 2-methyltetrahydrofuran (2-MeTHF).On the other hand, as lithium salts, known have a LiClO 4, LiBF 4, LiAsF 6, LiPF 6, LiCF 3SO 3, LiAlCl 4
On the other hand, as positive active material, utilize the insertion of lamellar compound or doping phenomenon and the material that forms receives much attention.
Even utilized in the material of insertion phenomenon of above-mentioned lamellar compound, chalcogenide has shown charge preferably.But the electromotive force of chalcogenide is low, even adopting under the situation of lithium metal as negative pole, uses the charging voltage maximum also can only reach about 2V, can not satisfy the characteristic of the high electromotive force of rechargeable nonaqueous electrolytic battery.
Utilize the active material of the insertion phenomenon of lamellar compound, except chalcogenide, also have other materials.V in the active material 6O 13, LiCoO 2, LiNiO 2, and the LiMn that utilizes the doping phenomenon 2O 4Deng the metal oxide compounds, because of the feature with high electromotive force receives much attention.Especially contain LiNiO 2The electromotive force and the theoretic energy density that just have about 4V as active material almost have the big like this value of per unit amount positive active material 1kWh/kg.
But, have the LiNiO of containing 2There is the low problem of charge and discharge circulation life in rechargeable nonaqueous electrolytic battery as the positive pole of active material.
On the other hand, Japan special permission open disclose for the clear 63-121258 of communique number adopt have bedded structure, general formula A xB yC zD wO 2Shown composite oxides are as the rechargeable nonaqueous electrolytic battery of positive pole.In the general formula, A is selected from least a in the alkali metal; B is a transition metal; C is selected from least a among Al, In, the Sn; D is selected from least a in the following element: (a) element in the 6th cycle of 2-of IIIb family except that Al, In, Sn, carbon, nitrogen, oxygen of the alkali metal beyond the A, the transition metal beyond (b) B, (c) IIa family element, (d), IVb family, Vb family, VIb family; X, y, z, w represent the number of 0.05≤x≤1.10,0.85≤y≤1.00,0.001≤z≤0.10,0.001≤w≤0.10.
But the rechargeable nonaqueous electrolytic battery of being put down in writing in the above-mentioned open communique can not obtain enough cycle life.
Summary of the invention
The object of the present invention is to provide a kind of rechargeable nonaqueous electrolytic battery that improves charge and discharge circulation life.
By the present invention, a kind of following rechargeable nonaqueous electrolytic battery is provided, it comprises positive pole, negative pole and the nonaqueous electrolyte that contains positive active material; Above-mentioned positive active material contains the oxide particle shown in oxide particle shown in the following formula (A) and the following formula (B), the ratio of the oxide particle shown in above-mentioned (A) in the above-mentioned positive active material surpasses 50 weight %, and above-mentioned positive active material satisfies following formula (1)-(5):
Li xNi yCo zM wO 2 (A)
Li aCo bM cO 2 (B)
Wherein M is the element more than a kind that is selected among Mn, B, Al and the Sn; Above-mentioned mol ratio x, y, z, w, a, b, c represent 0.95≤x≤1.05,0.7≤y≤0.95,0.05≤z≤0.3,0≤w≤0.1,0.95≤y+z+w≤1.05,0.95≤a≤1.05,0.95≤b≤1.05,0≤c≤0.05,0.95≤b+c≤1.05 respectively;
1.4≤(D N90/D N50)≤2 (1)
1.4≤(D N50/D N10)≤2 (2)
1.4≤(D C90/D C50)≤2 (3)
1.4≤(D C50/D C10)≤2 (4)
1.5≤(D N50/D C50)≤2.5(5)
Above-mentioned D N10, D N50, D N90Expression Li xNi yCo zM wO 2The volume accumulation frequency of particle is 10%, 50%, 90% particle diameter; Above-mentioned D C10, D C50, D C90Expression Li aCo bM cO 2The particle diameter of the volume accumulation frequency 10%, 50%, 90% of particle.
Description of drawings
Fig. 1 is the sectional view that shows the slim rechargeable nonaqueous electrolytic battery of rechargeable nonaqueous electrolytic battery one example of the present invention.
Fig. 2 is the amplification sectional view of the A portion of displayed map 1.
Fig. 3 is the sectional view that shows the square rechargeable nonaqueous electrolytic battery of rechargeable nonaqueous electrolytic battery one example of the present invention.
Embodiment
Example to rechargeable nonaqueous electrolytic battery of the present invention describes.
Rechargeable nonaqueous electrolytic battery of the present invention comprises container, be contained in the container and contain the electrode group of positive pole and negative pole and remain on nonaqueous electrolyte in the above-mentioned electrode group.
In this secondary cell, can between positive pole and negative pole, dispose barrier film, also can replace barrier film with the non-aqueous electrolyte layer of gel or solid, shaped.
Below just positive pole, negative pole, barrier film, nonaqueous electrolyte and container describe.
(1) positive pole
This positive pole comprises collector body and carries and is held in above-mentioned collector body single face or two-sided and contain the anodal layer of positive active material.
Above-mentioned positive active material contains the oxide particle shown in oxide particle shown in the following formula (A) and the following formula (B).The ratio of the oxide particle shown in above-mentioned (A) in the above-mentioned positive active material surpasses 50 weight %, and above-mentioned positive active material satisfies following formula (1)-(5):
Li xNi yCo zM wO 2 (A)
Li aCo bM cO 2 (B)
Wherein M is the element more than a kind that is selected among Mn, B, Al and the Sn; Above-mentioned mol ratio x, y, z, w, a, b, c represent 0.95≤x≤1.05,0.7≤y≤0.95,0.05≤z≤0.3,0≤w≤0.1,0.95≤y+z+w≤1.05,0.95≤a≤1.05,0.95≤b≤1.05,0≤c≤0.05,0.95≤b+c≤1.05 respectively;
14≤(D N90/D N50)≤2 (1)
1.4≤(D N50/D N10)≤2 (2)
1.4≤(D C90/D C50)≤2 (3)
1.4≤(D C50/D C10)≤2 (4)
1.5≤(D N50/D C50)≤2.5(5)
Above-mentioned D N10, D N50, D N90Represent Li respectively xNi yCo zM wO 2The particle diameter of the volume accumulation frequency 10%, 50%, 90% of particle; Above-mentioned D C10, D C50, D C90Represent Li respectively aCo bM cO 2The particle diameter of the volume accumulation frequency 10%, 50%, 90% of particle.
{ Li xNi yCo zM wO 2Particle (hereinafter referred to as nickel class particle) }
(Li)
It is reason according to following explanation that the mol ratio x of lithium is fixed in the above-mentioned scope: reduce if mol ratio x less than 0.95 o'clock, participates in discharging and recharging the lithium ion of reaction, discharge capacity descends.On the other hand, mol ratio x surpasses at 1.05 o'clock, because lithium ion has been sneaked into the Ni position, so discharge capacity descends.In addition, changes of crystal can reduce reactivity, so discharge voltage descends.The better scope of mol ratio x is 0.97≤x≤1.03.
(Ni)
It is reason according to following explanation that the mol ratio y of nickel is fixed in the above-mentioned scope: mol ratio y had the LiCoO of approaching less than 0.7 o'clock 2The characteristic of discharge capacity, so be difficult to reach the purpose that improves energy density.On the other hand, if mol ratio y surpasses at 0.95 o'clock, discharge capacity increases, but along with charge and discharge cycles, crystalline texture is decomposed easily.The better scope of mol ratio y is 0.75≤y≤0.9.
(Co)
It is reason according to following explanation that the mol ratio z of cobalt is fixed in the above-mentioned scope: if mol ratio z is less than 0.05 o'clock, and the stacked easy unrest of nickel dam, along with charge and discharge cycles, crystalline texture is decomposed easily.On the other hand, mol ratio z surpasses at 0.3 o'clock, in order to adjust stacked (the raising crystallinity) of Co layer, synthesis temperature must be adjusted to more than 850 ℃, but if improve synthesis temperature, Ni-O bond fission, deoxygenation takes place, and oxygen breaks away from from the R3m structure, and discharge capacity descends.The better scope of mol ratio z is 0.1≤z≤0.25.
(element M)
The element M performance suppresses the effect of the decomposition that charge and discharge cycles caused, and can form the pillar of supporting crystalline texture.In addition, by the interpolation element M, but the also decomposition of the nonaqueous electrolyte at inhibitory reaction interface.If mol ratio w surpasses at 0.1 o'clock, nickel is sneaked into the lithium ion position easily, and crystalline texture changes, and may make the heavy-current discharge difficulty, so mol ratio w is more fortunately below 0.1.The better scope of mol ratio w is 0≤w≤0.07, and better in 0≤w≤0.05, best scope is 0≤w≤0.03.In order to obtain the additive effect of enough element M, the lower limit of mol ratio w is preferably 0.001.
In element M, be preferably Sn.Adopt Sn as element M, can improve charge and discharge circulation life under the hot environment.This is considered to because promoted to form on anodal surface the reaction of the diaphragm that EC constitutes, and can suppress near (45 ℃) under the hot environment anodal reaction with gamma-butyrolacton.Li xNi yCo zM wO 2Particle is Li xNi yCo zO 2And Li 2SnO 3Mixture.
If when adopting Al or Mn, owing to improved Li as element M xNi yCo zSn wO 2The stability of the crystalline texture of particle discharges and recharges so can stablize in long-term circulation, further improves charge and discharge circulation life.
The reason that total (y+z+w) with mol ratio y, z, w is fixed in the above-mentioned scope describes.If (y+z+w) less than 0.95, the Li ratio in the particle increases, and generates the impurity that does not participate in discharging and recharging reaction, and discharge capacity descends.On the other hand, if (y+z+w) surpass 1.05, the Li amount that participates in reaction reduces, and discharge capacity descends.
With (D N90/ D N50) and (D N50/ D N10) to be each defined in the scope of 1.4-2 be reason according to following explanation: (D N90/ D N50) and (D N50/ D N10)=1 is meant that the particle size distribution of nickel class particle is single dispersion.If (D N90/ D N50) and (D N50/ D N10) less than 1.4, the narrow particle size distribution of nickel class particle, anodal activity substance filling amount is not enough, can not obtain high power capacity.
On the other hand, at (D N90/ D N50) surpass in 2 the nickel class particle, contain the particle of big particle diameter in a large number.The particle of big particle diameter is along with the suction storage and the release of lithium, and the contraction of expanding is big, so micronizing is carried out fast.Thus, if (D N90/ D N50) surpassing 2, the micronizing of nickel class particle is carried out, and is difficult to obtain the long-life.
At (D N50/ D N10) surpass in 2 the nickel class particle, contain fine particle in a large number.Such nickel class particle is reactive high to nonaqueous electrolyte, so carry out the oxidation Decomposition of nonaqueous electrolyte, charge and discharge circulation life shortens.
(D N90/ D N50) and (D N50/ D N10) better scope is 1.5-1.9 separately.
To surpass 50 weight % are reasons according to following explanation to the amount of nickel class particle in the positive active material: the amount of nickel class particle is when 50 weight % are following in the positive active material, and the discharge capacity of Unit Weight (specific capacity) descends.And if the amount of nickel class particle surpasses 90 weight %, may be difficult to obtain the large current density electrical characteristics that high discharge voltage is become reconciled, so the amount of nickel class particle surpasses in 50 weight %, the scope below 90 weight % more fortunately.
Better scope is 50-80 weight %.
{ Li aCo bM cO 2Particle (hereinafter referred to as cobalt class particle) }
It is reason according to following explanation that the mol ratio a of lithium is fixed in the above-mentioned scope: reduce if mol ratio a less than 0.95, participates in discharging and recharging the lithium ion of reaction, discharge capacity descends.If mol ratio a surpasses 1.05, be different from LiCoO owing to produced 2The impurity of structure is so discharge capacity descends.The better scope of mol ratio a is 0.97≤a≤1.03.
(Co)
It is reason according to following explanation that the mol ratio b of cobalt is fixed on above-mentioned scope: if mol ratio b is less than 0.95, (a/b) than corresponding increase, the lithium ion that participates in discharging and recharging reaction reduces, and discharge capacity descends.If mol ratio b surpasses 1.05, (a/b) diminish than corresponding, generate and discharge and recharge irrelevant impurity, discharge capacity descends.The better scope of mol ratio b is 0.97≤b≤1.03.
(element M)
Element M can suppress or control the decomposition reaction of nonaqueous electrolyte, and the effect of playing the structure reinforcement of the decomposition that suppresses the caused crystalline texture of charge and discharge cycles.When not changing,, improve cycle characteristics owing to strengthened crystalline texture for the valence mumber that discharges and recharges element M.But mol ratio c surpasses at 0.05 o'clock, and the Co amount descends relatively, and the lithium amount that participates in cell reaction is not enough, and discharge capacity reduces.Thus, below 0.05, the better scope of mol ratio c is 0.001≤c≤0.03 to mol ratio c more fortunately.
In element M, be preferably Sn.Adopt Sn as element M, can improve charge and discharge circulation life under the hot environment.This is considered to because promoted to form on anodal surface the reaction of the diaphragm that EC constitutes, and can suppress near (45 ℃) under the hot environment anodal reaction with gamma-butyrolacton.Li aCo bSn cO 2Particle is Li aCo bO 2And Li 2SnO 3Mixture.
The reason that total (b+c) with mol ratio b, c is fixed in the above-mentioned scope describes.If (b+c) less than 0.95, the lithium ratio in the particle increases, and generates the impurity that does not participate in discharging and recharging reaction, and discharge capacity descends.If (b+c) surpass at 1.05 o'clock, the Li amount that participates in reaction reduces, and discharge capacity descends.
With (D C90/ D C50) and (D C50/ D C10) to be each defined in the scope of 1.4-2 be reason according to following explanation: D C90/ D C50) and (D C50/ D C10)=1 is meant that the particle size distribution of cobalt class particle is single dispersion.If (D C90/ D C50) and (D C50/ D C10) all less than 1.4, the narrow particle size distribution of cobalt class particle, anodal activity substance filling amount is not enough, can not obtain high power capacity.
On the other hand, at (D C90/ D C50) surpass in 2 the cobalt class particle, contain the particle of big particle diameter in a large number.Such cobalt class particle, the lithium diffusion velocity is slow, so cause the large current density electrical characteristics to descend.
At (D C50/ D C10) surpass in 2 the cobalt class particle, contain fine particle in a large number.The reactive height of such cobalt class particle and nonaqueous electrolyte, so carry out the oxidation Decomposition of nonaqueous electrolyte, charge and discharge circulation life shortens.
(D C90/ D C50) and (D C50/ D C10) better scope is 1.5-1.9 separately.
The D of cobalt class particle C50More fortunately 0.2 μ m above, below the 30 μ m.This is because due to the following reason: if D C50Less than 0.2 μ m, the crystalline growth of cobalt class particle is not enough, may be difficult to obtain enough discharge capacities.In addition, if D C50Surpass 30 μ m, during not only anodal the manufacturing, be difficult to obtain anodal uniformly surface, and because particle diameter is big, the surface area of per unit volume reduces, reactive decline.D C50Better scope is more than the 1 μ m, below the 15 μ m.
When the volume of above-mentioned nickel class particle and cobalt class particle accumulation frequency 10%, 50%, 90% is satisfied concerning of above-mentioned (1)-(4), with particle diameter D (D N50/ D C50) reason that fixes in the scope of 1.5-2.5 describes.If (D N50/ D C50) more than 1, less than 1.5, the particle size distribution of the particle size distribution of nickel class particle and cobalt class particle is closely similar, the charge and discharge circulation life shortening is shunk in the expansion that is difficult to when suppressing nickel class particle and inhale storage and discharge lithium with cobalt class particle.In addition, cobalt class particle more can improve average discharge volt than nickel class particle, and begins can easily carry out the suction storage of lithium and discharge from the discharge initial stage.
(D N50/ D C50) less than 1 o'clock, the particle size distribution of cobalt class particle was positioned at big particle diameter side than the particle size distribution of nickel class particle, so the lithium diffusion velocity of cobalt class particle is impaired, large current density electrical characteristics variation.
If (D N50/ D C50) surpassing at 2.5 o'clock, the particle size distribution of nickel class particle more obviously is positioned at big particle diameter side than the particle size distribution of cobalt class particle, so reactive difference of the reactivity of nickel class particle and cobalt class particle is obvious.Consequently: appearance is inhomogeneous easily to discharge and recharge reaction on the positive pole, and charge and discharge circulation life shortens.When being modulated into paste, can influence the dispersiveness or the coating of paste, be difficult to make the positive pole of stay in grade as if this positive active material of use and with it.(D N50/ D C50) better scope is 1.6-2.4.
As positive active material, can respectively use a kind of nickel class particle and a kind of cobalt class particle, also can use and form the different nickel class particles more than 2 kinds, perhaps use and form the different cobalt class particles more than 2 kinds.
Above-mentioned positive pole for example can make by the method for following (i)-(iii) explanation.
(i) positive active material, conductive agent and binding agent are suspended in the appropriate solvent, the mixture slurries that make are coated on the collector body, after the drying, suppress, be cut into the size of hope, make positive pole.At this moment, better coating weight with collector body back starching liquid is controlled at 100-400g/cm 2Scope in.
(ii) positive active material, conductive agent and binding agent are mixed, the mixture that makes is configured as graininess after, the one-tenth particle that makes pressed be attached on the collector body and form anodal.
(iii) positive active material, conductive agent and binding agent are mixed, the mixture that makes is configured as sheet after, the matrix band that makes pressed be attached on the collector body and form anodal.
As above-mentioned conductive agent, carbon black, graphite etc. such as for example available acetylene black or kitchen are black.
As above-mentioned binding agent, for example available containing gathers inclined to one side 1, the copolymer of 1-difluoroethylene (PVdF), vinylidene fluoride (VdF), tetrafluoroethene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), perfluoroalkyl vinyl ether (PFA) or terpolymer etc. as monomer component.
The proportioning of positive active material, conductive agent and binding agent is: positive active material is that 80-95 weight %, conductive agent are that 3-10 weight %, binding agent are 2-10 weight %.
As above-mentioned collector body, for example available aluminium foil, stainless steel foil, titanium foil are considered hot strength, electrochemical stability and the flexibility when rolling etc., the most handy aluminium foil.This moment paper tinsel thickness more fortunately 10 μ m above, below the 30 μ m.
Collector body can also use other porose collector body such as perforated metal, expansion alloy except the paper tinsel shape.
(2) negative pole
This negative pole comprise collector body and carry be held in above-mentioned collector body single face or two-sided on negative electrode layer.
Negative electrode layer contains the compound of inhaling storage and discharging lithium ion or lithium atom.As this compound, material with carbon element that available electroconductive polymer (for example polyacetals, polyacetylene, polypyrrole etc.), organic substance roasting body are such etc.
Above-mentioned material with carbon element can be regulated the characteristic of material with carbon element by raw material type and roasting method.As the concrete example of material with carbon element, available graphite-like material with carbon element, be mixed with the material with carbon element etc. that material with carbon element, the crystallizing layer of graphite crystallization part and amorphous fraction got the mixed and disorderly layer structure of no regularity in stacked.
Above-mentioned negative pole can make by the method for following (I)-(III) explanation.
(I) compound and the binding agent inhaling storage and discharge lithium ion or lithium atom are suspended in the appropriate solvent, the mixture slurries that make are coated on the collector body, after the drying, suppress, be cut into the size of hope and form negative pole.Be coated on the coating weight 50-200g/m more fortunately of the slurries of collector body single face this moment 2
(II) will inhale storage and discharge lithium ion or the compound and the binding agent of lithium atom mix, the mixture that makes is configured as graininess after, the particle that makes pressed be attached on the collector body and form negative pole.
(III) will inhale storage and discharge lithium ion or the compound and the binding agent of lithium atom mix, the mixture that makes is configured as sheet after, the matrix band that makes pressed be attached on the collector body and form negative pole.
As above-mentioned binding agent, the identical binding agent of binding agent that available and above-mentioned positive pole has illustrated.
As the collector body of above-mentioned negative pole, for example available Copper Foil, nickel foil etc.Consider electrochemical stability and flexibility, the most handy Copper Foil.The paper tinsel thickness of this moment more fortunately 8 μ m above, below the 20 μ m.Collector body also can use other porose collector body such as perforated metal, expansion alloy except the paper tinsel shape.
(3) nonaqueous electrolyte
As nonaqueous electrolyte, can use the electrolyte that has aqueous or gelatinous form in fact.Aqueous nonaqueous electrolyte contains nonaqueous solvents and is dissolved in the interior electrolyte of nonaqueous solvents.On the other hand, the gel nonaqueous electrolyte contains aqueous nonaqueous electrolyte, makes the gelating agent of aqueous nonaqueous electrolyte gelation.As gelating agent, available poly(ethylene oxide), polyacrylonitrile etc.
As above-mentioned nonaqueous solvents, available propylene carbonate (PC), carbonic acid ethylidene ester (EC), ethylmethyl carbonate (EMC), dimethyl carbonate (DMC), carbonic acid diethyl ester (DEC), diethoxyethane (DEE), gamma-butyrolacton (γ-BL), oxolane (THF), 2-methyltetrahydrofuran (2-MeTHF), 1,3-two  alkane, 1,3-dimethoxy propane etc.The kind of the nonaqueous solvents that uses can be a kind or more than 2 kinds.
As above-mentioned electrolyte, for example available lithium perchlorate (LiClO 4), tetrafluoride lithium borate (LiBF 4), arsenic hexafluoride lithium (LiAsF 6), trifluoromethayl sulfonic acid lithium (LiCF 3SO 3), bis trifluoromethyl sulfimide lithium (LiN (CF 3SO 2) 2), LiN (C 2F 5SO 2) 2, lithium salts such as aluminum tetrachloride lithium.The electrolytical kind of using can be a kind of, also can be more than 2 kinds.
The meltage of above-mentioned electrolyte in above-mentioned nonaqueous solvents is more fortunately in the scope of 0.5-1.5 mole/L.
(4) barrier film
This barrier film is formed by porous matter sheet.
For example available porous film of above-mentioned porous matter sheet or nonwoven fabrics.Above-mentioned porous matter sheet better is made of at least a material that is selected from polyolefin and the cellulose.As said polyolefins, available polyethylene, polypropylene.Wherein constitute or, be desirable for the stability that can improve secondary cell by the porous film that polyethylene and polypropylene constitute by polyethylene or polypropylene.
(5) container
The shape of container can make round-ended cylinder shape, end square tube shape has been arranged, bag shape, cup-shaped etc.
Said vesse can be formed by resin, the matrix band that contains resin bed, metallic plate and metallic film etc.
As above-mentioned resin, the such polyolefin of available polyethylene, polypropylene, nylon etc.
Contained resin bed can be formed by polyethylene, polypropylene, nylon etc. in above-mentioned.As above-mentioned matrix band, more handy with metal level, be configured in the integrated matrix band that forms of protective layer on the above-mentioned metal level two sides.Above-mentioned metal level is formed by aluminium, stainless steel, iron, copper, nickel etc.Wherein, aluminium more handy light weight, that water resistance is high.Above-mentioned metal level can be formed by a kind of metal, and also the metal that can be formed by the metal-integral more than 2 kinds forms.In the above-mentioned 2 layers protective layer, the protective layer that joins with the outside plays the effect that prevents that above-mentioned metal level is impaired.This outer protection layer is formed by a kind of resin bed or the resin bed more than 2 kinds.On the other hand, the internal protection layer plays the effect that above-mentioned metal level is avoided the corrosion of nonaqueous electrolyte.This internal protection layer can be formed, also can be formed by the resin bed more than 2 kinds by a kind of resin bed.The surface of internal protection layer can be provided with thermoplastic resin.
Above-mentioned metallic plate and above-mentioned metallic film can be formed by iron, stainless steel, aluminium.
With reference to the accompanying drawings 1 and 2, an example of rechargeable nonaqueous electrolytic battery of the present invention, slim rechargeable nonaqueous electrolytic battery are described.
Fig. 1 is the sectional view of slim rechargeable nonaqueous electrolytic battery that shows an example of rechargeable nonaqueous electrolytic battery of the present invention; Fig. 2 is the amplification sectional view of the A portion of displayed map 1.As shown in Figure 1, the electrode group 2 of packing in the container 1.
Above-mentioned electrode group 2 has the structure that the sandwich that will be made of positive pole, barrier film and negative pole is rolled into flat pattern.Above-mentioned sandwich, carry out lamination by following order as shown in Figure 2 and form: (from the downside of figure) barrier film 3, have anodal layer 4, positive electrode collector 5 and anodal layer 4 positive pole 6, barrier film 3, the negative pole 9 with negative electrode layer 7, negative electrode collector 8 and negative electrode layer 7, barrier film 3, have anodal layer 4, positive electrode collector 5 and anodal layer 4 positive pole 6, barrier film 3, have the negative pole 9 of negative electrode layer 7 and negative electrode collector 8.One end of banded positive wire 10 is connected with the above-mentioned positive electrode collector 5 of above-mentioned anodal group 2, and the other end of this lead-in wire is drawn by said vesse 1.On the other hand, an end of banded negative wire 11 is connected with the above-mentioned negative electrode collector 8 of negative pole group 2, and its other end is drawn by said vesse.
In above-mentioned Fig. 1, Fig. 2, adopted by barrier film positive pole and negative pole have been rolled into the electrode group of flat pattern, also can use by barrier film and anodal and negative pole be folded the electrode group that forms or the electrode group that positive pole and negative pole lamination formed by barrier film etc.
Fig. 3 has shown that the present invention is applicable to the figure of an example of prismatic nonaqueous electrolyte secondary battery.
As shown in Figure 3, have in the end rectangle cylindrical container 12 at for example aluminum metal and put into electrode group 13.Electrode group 13 is by successively that positive pole 14, barrier film 15 and negative pole 16 is stacked, is rolled into flat pattern and forms.Near the barrier film 17 that has peristome the central authorities is configured in the top of electrode group 13.
Nonaqueous electrolyte is maintained in the electrode group 13.Have opened circular port near explosion-proof 18a of mechanism and the central authorities hush panel 18b by laser welding on the peristome of container 12.Negative terminal 19 by seal arrangement on the circular port of hush panel 18b.The negative plate 20 of drawing from negative pole 16 is welded on the lower end of negative terminal 19.On the other hand, positive plate (not having diagram) is connected with the container 12 of the band positive terminal of holding concurrently.
The positive active material of above-described rechargeable nonaqueous electrolytic battery of the present invention contains Li aCo bM cO 2Particle (cobalt class particle) and surpass the Li of 50 weight % xNi yCo zM wO 2Particle (nickel class particle), and satisfy above-mentioned (1)-(5) formula.
Adopt above-mentioned secondary cell, can guarantee high discharge voltage and good large current density electrical characteristics, and improve positive active material packed density and charge and discharge circulation life.
That is,, can improve the discharge capacity (specific capacity) of per unit weight by will in positive active material, surpassing 50 weight % by the content of nickel class particle.
By (D with nickel class particle N90/ D N50) be controlled in the scope of 1.4-2, can reduce in the nickel class particle along with the extremely big particle of contraction that expands that discharges is store in the suction of lithium.On the other hand, by (D with cobalt class particle C90/ D C50) be controlled in the scope of 1.4-2, can guarantee the high lithium diffusion velocity of positive active material.
By (D with nickel class particle N50/ D N10) and (D of cobalt class particle C50/ D C10) be controlled in the scope of 1.4-2, because positive electrode active material confrontation nonaqueous electrolyte reactive low, can suppress the oxidation Decomposition of nonaqueous electrolyte.
By with (D N50/ D C50) be controlled in the scope of 1.5-2.5, owing to make the particle size distribution of positive active material have proper width, so can improve the packed density of positive active material.Simultaneously, owing to the lithium that is accompanied by that utilizes the littler cobalt class particle of expansion degree of shrinkage to suppress nickel class particle is inhaled the expansion contraction that the carrying out of storage and release produces, so can suppress the micronizing of nickel class particle.
Thus, by the present invention, can realize satisfying simultaneously the rechargeable nonaqueous electrolytic battery of discharge voltage, specific capacity, large current density electrical characteristics, active material packed density and charge and discharge circulation life.
Below with reference to accompanying drawing embodiments of the invention are elaborated.
(mensuration of anodal specific capacity (mAh/g))
At first, the weight ratio shown in the following table 1 is with the LiCoO of cobalt class particle 2The LiNi of particle and nickel class particle 0.81Co 0.19O 2Mix particles is prepared sample 1-7.
Adopt sample 1-7 as active material, make the effect utmost point.Promptly, with the agate altar polytetrafluoroethylene (PTFE) of 0.03 weight portion, the acetylene black (AB) of 0.06 weight portion, the active material of 1 weight portion are mixed, after utilizing roll-in to make its sheetization, press the nickel system that is attached to online, make the effect utmost point of the 1cm * 1cm of the active material that contains 0.05g approximately.
Press the nickel system that is attached to online on the lithium paper tinsel, make the reference utmost point of 2cm * 2cm the utmost point and 0.5cm * 0.5cm.By glass filter, make the effect utmost point and the utmost point disposed in opposite directions so that with reference to the utmost point with to the utmost point with act on the utmost point and do not contact and be configured, make battery (cell).
Above-mentioned battery is linked to each other with the glass container that can switch on by the metallicity lead, fill with nonaqueous electrolytic solution (be dissolved in the LiBF4 of 1.5mol/L in the nonaqueous solvents that ethylene carbonate (EC) and gamma-butyrolacton is mixed with volume ratio 1: 2 and form) to the above-mentioned battery of submergence, sealing.Operation is to carry out in the glove box of dew point-80 ℃.
Charging is to begin to charge with the constant voltage of 4.25V with the constant current charge of 1mA to 4.25V, moment of reaching 4.25V.The total time of constant current charge and constant-potential charge is 20 hours.Discharge is to carry out with 1.0mA, and the discharge capacity that will reach 3.0V is decided to be discharge capacity.The value that discharge capacity is obtained divided by the weight of the active material in the effect extremely is decided to be specific capacity (mAh/g), is presented in the following table 1.In the table 1, also shown the LiCoO that can obtain with 1g 2The weight of sample 1-7 of the same discharge capacity of discharge capacity.
Table 1
Cobalt class particle (LiCoO 2) (weight %) Nickel class particle (LiNi 0.81Co 0.19O 2) (weight %) Discharge capacity (mAh/g) Form LiCoO with 1g 2The sample weight (g) of the equal discharge capacity of discharge capacity
Sample 1 0 100 190 0.789
Sample 2 10 90 186 0.806
Sample 3 30 70 178 0.843
Sample 4 40 60 174 0.862
Sample 5 50 50 170 0.882
Sample 6 60 40 166 0.904
Sample 7 100 0 150 1
As known from Table 1: the use level of nickel class particle is surpassed the sample 1-4 of 50 weight %, and 5-7 compares with sample, and (mAh/g) is higher for discharge capacity, in addition, and with LiCoO 2(sample 7) compared, and can obtain high discharge capacity with less amount.
In following embodiment, the influence that the different specific capacity differences that cause of the mixing ratio of cobalt class particle and nickel class particle produce is few, the coating weight of negative pole is controlled at necessarily, cooperate the mixing ratio of positive active material and change anodal coating weight (positive active material amount), can carry out the manufacturing of battery.
(embodiment 1)
(anodal makes)
As cobalt class particle, prepare volume accumulation frequency 10% particle diameter D C10Be 1.9 μ m, volume accumulation frequency 50% particle diameter D C50Be 3.3 μ m, volume accumulation frequency 90% particle diameter D C90Be the LiCoO of 5.7 μ m 2Particle.As nickel class particle, prepare volume accumulation frequency 10% particle diameter D N10Be 4 μ m, volume accumulation frequency 50% particle diameter D N50Be 7 μ m, volume accumulation frequency 90% particle diameter D N90Be the LiNi of 11.6 μ m 0.81Co 0.19O 2Particle.
Shown (D in the table 2 N50/ D N10), (D N90/ D N50), (D C50/ D C10), (D C90/ D C50) and (D N50/ D C50).Volume accumulation frequency 10%, 50%, 90% particle diameter is measured by the method for following explanation.That is, by laser diffraction and scattering method respectively to the possessive volume of nickel class particle and its particle diameter of cobalt class particle assay and the particle in each granularity zone.The volume accumulation that granularity is interregional, 10% o'clock the particle diameter that will reach whole distribution is decided to be the particle diameter of volume accumulation frequency 10%, 50% o'clock particle diameter is decided to be the particle diameter that volume is accumulated frequency 50%, 90% o'clock particle diameter is decided to be the particle diameter of volume accumulation frequency 90%.
At first, with the poly-inclined to one side vinylidene fluoride of 3 weight portions (the Wu Yu chemistry industrial producers name of an article: #1100) be dissolved in the N-methyl pyrrolidone of 25 weight portions.Above-mentioned LiCoO with 8.9 weight portions 2The above-mentioned LiNi of particle and 80.1 weight portions 0.81Co 0.19O 2The material that mix particles forms is as positive active material, (ロ Application ザ company makes trade name: KS6) be added on poly-inclined to one side 1 with the graphite of the conductive material of this positive active material and 8 weight portions, in the 1-difluoroethylene solution, mix, make anodal slurries with dissolvers and ball mill.Use the mould coating machine, at certain intervals these slurries are coated on the two sides of aluminium foil of thickness 15 μ m, after the drying, with certain line pressure (kgf/cm) compacting, severing makes the positive pole of band shape (reel shape).Calculate the density (active material density: g/cm of per unit volume active material from anodal layer thickness 3), its result is illustrated in the following table 3.
In table 2, closing note has LiNi 0.81Co 0.19O 2The weight rate W of particle N(weight %) and LiCoO 2The weight rate W of particle c(weight %).
(making of negative pole)
In mesophase pitch based carbon fiber powder (manufacturing of ペ ト カ company) 100 weight portions, add the powdered graphite (ロ Application ザ company makes trade name KS15) of 10 weight portions, and mix, add the phenylethylene/butadiene latex (name of an article L1571 of manufacturer of industrial group of Asahi Chemical Industry, solid constituent are 48 weight %) of 4.2 weight portions, the aqueous solution (solid constituent 1 weight %) of the carboxy methyl cellulose as tackifier of 130 weight portions (the first industrial pharmacy name of an article BSH12 of manufacturer), the distilled water of 20 weight portions again, mix the modulation slurries.
Utilize the mould coating machine, these slurries be coated on the two sides of Copper Foil of thickness 10 μ m at certain intervals, after the drying, compacting, severing makes the negative pole of band shape (reel shape).
(manufacturing of nonaqueous electrolytic solution)
1.5 moles/LLiBF4 is dissolved in the nonaqueous solvents that forms with 1: 2 mixed carbonic acid ethyl (EC) of volume ratio and gamma-butyrolacton (GBL), makes nonaqueous electrolytic solution.
(assembling of battery)
Successively the barrier film of above-mentioned positive pole, polypropylene system and above-mentioned negative pole are carried out stacked after, be rolled into flat, 90 ℃ of compactings of carrying out for 30 seconds, make the electrode group; On the above-mentioned positive pole, will be connected on the position of regulation in advance as the aluminum strip supersonic welding of thickness 100 μ m, the length 70mm of the collector body of positive pole and will prevent that the polyimides system boundary belt that short circuit is used from sticking to the welding position; On negative pole, will be connected on the position of regulation in advance as the nickel bar supersonic welding of thickness 100 μ m, the length 70mm of the collector plate of negative pole and will prevent that the polyimides system boundary belt that short circuit is used from sticking to the welding position.
On the other hand, carry out cup-shaped by the stacked film that covers the thickness 0.1mm that the outside forms to electrode group one side that covers aluminium foil with polyethylene, with nylon and be shaped, prepare the container that forms therefrom.
Above-mentioned electrode group and above-mentioned electrolyte are put into said vesse, seal, be assembled into slim rechargeable nonaqueous electrolytic battery (wide 35mm, long 62mm).Begin to finish from injecting the solution operation, all under Ar atmosphere, be controlled in the glove box of dew point-80 ℃ and carry out to sealing process.
(embodiment 2)
Except with the LiCoO in the positive pole 2The use level of particle adjusts to 26.7 weight portions, with LiNi 0.81Co 0.19O 2The use level of particle is adjusted to beyond 62.3 weight portions, with the foregoing description 1 explanation like that, make slim rechargeable nonaqueous electrolytic battery.
(embodiment 3)
Except with the LiCoO in the positive pole 2The use level of particle adjusts to 35.6 weight portions, with LiNi 0.81Co 0.19O 2The use level of particle is adjusted to beyond 53.4 weight portions, with the foregoing description 1 explanation like that, make slim rechargeable nonaqueous electrolytic battery.
(embodiment 4)
Except as nickel class particle, adopt D N10Be 5.3 μ m, D N50Be 7.7 μ m, D N90Be the LiNi of 11.1 μ m 0.81Co 0.19O 2Particle is also with the LiCoO in the positive pole 2The use level of particle adjusts to 26.7 weight portions, with LiNi 0.81Co 0.19O 2The use level of particle is adjusted to beyond 62.3 weight portions, with the foregoing description 1 explanation like that, make slim rechargeable nonaqueous electrolytic battery.
(embodiment 5)
Except as nickel class particle, adopt D N10Be 3.3 μ m, D N50Be 6.5 μ m, D N90Be the LiNi of 12.5 μ m 0.81Co 0.19O 2Particle is also with the LiCoO in the positive pole 2The use level of particle adjusts to 26.7 weight portions, with LiNi 0.81Co 0.19O 2The use level of particle is adjusted to beyond 62.3 weight portions, with the foregoing description 1 explanation like that, make slim rechargeable nonaqueous electrolytic battery.
(embodiment 6)
Except as cobalt class particle, adopt D C10Be 2.7 μ m, D C50Be 3.9 μ m, D C90Be the LiCoO of 5.8 μ m 2Particle is also with the LiCoO in the positive pole 2The use level of particle adjusts to 26.7 weight portions, with LiNi 0.81Co 0.19O 2The use level of particle is adjusted to beyond 62.3 weight portions, with the foregoing description 1 explanation like that, make slim rechargeable nonaqueous electrolytic battery.
(embodiment 7)
Except as cobalt class particle, adopt D C10Be 1.6 μ m, D C50Be 3 μ m, D C90Be the LiCoO of 5.7 μ m 2Particle is also with the LiCoO in the positive pole 2The use level of particle adjusts to 26.7 weight portions, with LiNi 0.81Co 0.19O 2The use level of particle is adjusted to beyond 62.3 weight portions, with the foregoing description 1 explanation like that, make slim rechargeable nonaqueous electrolytic battery.
(embodiment 8)
Except as nickel class particle, adopt D N10Be 4.7 μ m, D N50Be 8 μ m, D N90Be the LiNi of 13.6 μ m 0.81Co 0.19O 2Particle is also with the LiCoO in the positive pole 2The use level of particle adjusts to 26.7 weight portions, with LiNi 0.81Co 0.19O 2The use level of particle is adjusted to beyond 62.3 weight portions, with the foregoing description 1 explanation like that, make slim rechargeable nonaqueous electrolytic battery.
(embodiment 9)
Except as nickel class particle, adopt D N10Be 2.9 μ m, D N50Be 5.2 μ m, D N90Be the LiNi of 8.9 μ m 0.81Co 0.19O 2Particle is also with the LiCoO in the positive pole 2The use level of particle adjusts to 26.7 weight portions, with LiNi 0.81Co 0.19O 2The use level of particle is adjusted to beyond 62.3 weight portions, with the foregoing description 1 explanation like that, make slim rechargeable nonaqueous electrolytic battery.
(embodiment 10)
Except as cobalt class particle, adopt D C10Be 1.9 μ m, D C50Be 3.3 μ m, D C90Be the LiCo of 5.7 μ m 0.97Sn 0.03O 2Particle is (with LiCoO 2When being decided to be 100 weight portions, contain the Li of 3.1 weight portions 2SnO 3Mixture), also with the LiCo in the positive pole 0.97Sn 0.03O 2The particle use level adjusts to 26.7 weight portions, with LiNi 0.81Co 0.19O 2The use level of particle is adjusted to beyond 62.3 weight portions, with the foregoing description 1 explanation like that, make slim rechargeable nonaqueous electrolytic battery.
(embodiment 11)
Except as nickel class particle, adopt D N10Be 4 μ m, D N50Be 7 μ m, D N90Be the LiNi of 11.6 μ m 0.78Co 0.18Sn 0.03O 2Particle is (with LiNi 0.81Co 0.19O 2When being decided to be 100 weight portions, contain the Li of 3.1 weight portions 2SnO 3Mixture), also with the LiCoO in the positive pole 2The use level of particle adjusts to 26.7 weight portions, with LiNi 0.78Co 0.18Sn 0.03O 2The use level of particle is adjusted to beyond 62.3 weight portions, with the foregoing description 1 explanation like that, make slim rechargeable nonaqueous electrolytic battery.
(embodiment 12)
Except as nickel class particle, adopt D N10Be 4 μ m, D N50Be 7 μ m, D N90Be the LiNi of 11.6 μ m 0.76Co 0.18Al 0.06O 2Beyond the particle, with the foregoing description 1 explanation like that, make slim rechargeable nonaqueous electrolytic battery.
(embodiment 13)
Except as nickel class particle, adopt D N10Be 4 μ m, D N50Be 7 μ m, D N90Be the LiNi of 11.6 μ m 0.76Co 0.18Mn 0.06O 2Beyond the particle, with the foregoing description 1 explanation like that, make slim rechargeable nonaqueous electrolytic battery.
(comparative example 1)
Except as positive active material, only adopt D N10Be 4 μ m, D N50Be 7 μ m, D N90Be the LiNi of 11.6 μ m 0.81Co 0.19O 2Beyond the particle, with the foregoing description 1 explanation like that, make slim rechargeable nonaqueous electrolytic battery.
(comparative example 2)
Except with the LiCoO in the positive pole 2The use level of particle be decided to be 53.4 weight portions, with LiNi 0.81Co 0.19O 2The use level of particle is decided to be beyond 35.6 weight portions, with the foregoing description 1 explanation like that, make slim rechargeable nonaqueous electrolytic battery.
(comparative example 3)
Except as cobalt class particle, adopt D C10Be 2.7 μ m, D C50Be 3.4 μ m, D C90Be the LiCoO of 4.3 μ m 2Particle is also with the LiCoO in the positive pole 2The particle use level adjusts to 26.7 weight portions, with LiNi 0.81Co 0.19O 2The use level of particle is adjusted to beyond 62.3 weight portions, with the foregoing description 1 explanation like that, make slim rechargeable nonaqueous electrolytic battery.
(comparative example 4)
Except as cobalt class particle, adopt D C10Be 1.5 μ m, D C50Be 3.5 μ m, D C90Be the LiCoO of 8.4 μ m 2Particle is also with the LiCoO in the positive pole 2The particle use level adjusts to 26.7 weight portions, with LiNi 0.81Co 0.19O 2The use level of particle is adjusted to beyond 62.3 weight portions, with the foregoing description 1 explanation like that, make slim rechargeable nonaqueous electrolytic battery.
(comparative example 5)
Except as cobalt class particle, adopt D C10Be 3.8 μ m, D C50Be 6.1 μ m, D C90Be the LiCoO of 10 μ m 2Particle is also with the LiCoO in the positive pole 2The particle use level adjusts to 26.7 weight portions, with LiNi 0.81Co 0.19O 2The use level of particle is adjusted to beyond 62.3 weight portions, with the foregoing description 1 explanation like that, make slim rechargeable nonaqueous electrolytic battery.
(comparative example 6)
Except as cobalt class particle, adopt D C10Be 1.5 μ m, D C50Be 2.6 μ m, D C90Be the LiCoO of 4.5 μ m 2Particle is also with the LiCoO in the positive pole 2The particle use level adjusts to 26.7 weight portions, with LiNi 0.81Co 0.19O 2The use level of particle is adjusted to beyond 62.3 weight portions, with the foregoing description 1 explanation like that, make slim rechargeable nonaqueous electrolytic battery.
(comparative example 7)
Except as positive active material, only adopt D C10Be 1.9 μ m, D C50Be 3.3 μ m, D C90Be the LiCoO of 5.7 μ m 2Beyond the particle, with the foregoing description 1 explanation like that, make slim rechargeable nonaqueous electrolytic battery.
To the embodiment 1-13 that makes and the secondary cell of comparative example 1-7, measure the capacity of 0.2C, capacity, cell thickness, average discharge volt, energy density and the cycle life of 1C in order to method down, its result is illustrated in the following table 3.
(rated capacity)
To the secondary cell that assembles, under 20 ℃, amount to 12 hours primary charging, its process is,,, charges with constant voltage after reaching 4.2V to 4.2V with the constant current charge of 140mA (being equivalent to 0.2CMA) again.Discharge capacity when mensuration is discharged to 3.0V with the constant current of 140mA, the rated capacity when discharging as 0.2C, its result is illustrated in the following table 3.
(discharge capacity of 1.0C)
To 4.2V, amount to charging in 12 hours with constant voltage 4.2V with the constant current charge of 140mA again.Measure the discharge capacity when constant current is discharged to 3.0V then with 1CmA (700mA), the capacity when discharging as 1.0C, its result is illustrated in the following table 3.
(cell thickness is measured and energy density)
To 4.2V, the constant voltage with 4.2V amounts to charging in 12 hours again with the constant current charge of 140mA.Measure 4.2V cell thickness constantly.Average voltage is obtained by the integrated value that is discharged to the discharge curve of 3.0V with 0.2CmA (140mA).Volume energy density is obtained by cell widths (35mm), length (62mm), the cell thickness that records and the average voltage of the collector plate of removing anodal and negative pole.Its result is illustrated in the table 3.
(cycle life)
With 1C (700mA) constant current charge to 4.2V, reach 4.2V after, amount to 3 hours charging again with constant voltage, be discharged to 3.0V with 1C.Measure 80% the period that discharge capacity reaches the 1st cyclic discharge capacity, with its result as cycle life and be illustrated in the following table 3.
Table 2
Weight ratio W N∶W C(weight %) D N50/D N10 D N90/D N50 D C50/D C10 D C90/D C50 D N50/D C50
Embodiment 1 90∶10 1.75 1.66 1.7 1.73 2.13
Embodiment 2 70∶30 1.75 1.66 1.7 1.73 2.13
Embodiment 3 60∶40 1.75 1.66 1.7 1.73 2.13
Embodiment 4 70∶30 1.45 1.44 1.7 1.73 2.33
Embodiment 5 70∶30 1.71 1.93 1.7 1.73 1.97
Embodiment 6 70∶30 1.75 1.66 1.45 1.48 1.78
Embodiment 7 70∶30 1.75 1.66 1.89 1.93 2.37
Embodiment 8 70∶30 1.69 1.69 1.7 1.73 2.43
Embodiment 9 70∶30 1.78 1.72 1.7 1.73 1.57
Embodiment 10 70∶30 1.75 1.66 1.7 1.73 2.13
Embodiment 11 70∶30 1.75 1.66 1.7 1.73 2.13
Embodiment 12 90∶10 1.75 1.66 1.7 1.73 2.13
Embodiment 13 90∶10 1.75 1.66 1.7 1.73 2.13
Comparative example 1 100∶0 1.75 1.66 - - -
Comparative example 2 40∶60 1.75 1.66 1.7 1.73 2.13
Comparative example 3 70∶30 1.75 1.66 1.28 1.25 2.05
Comparative example 4 70∶30 1.75 1.66 2.34 2.4 1.98
Comparative example 5 70∶30 1.75 1.66 1.62 1.65 1.15
Comparative example 6 70∶30 1.75 1.66 1.77 1.73 2.68
Comparative example 7 0∶100 - - 1.7 1.73 -
Table 3
Active material density (g/cm 3) 0.2C capacity (mAh) 1C capacity (mAh) Cell thickness (mm) Average voltage (V) Energy density (Wh/L) Cycle life
Embodiment 1 3.2 710 675 3.75 3.74 326 490
Embodiment 2 3.27 718 686 3.79 3.77 329 634
Embodiment 3 3.23 706 678 3.83 3.79 322 560
Embodiment 4 3.21 709 677 3.79 3.77 325 536
Embodiment 5 3.26 710 678 3.79 3.77 325 542
Embodiment 6 3.24 715 683 3.79 3.77 328 521
Embodiment 7 3.27 703 671 3.78 3.77 323 555
Embodiment 8 3.29 706 674 3.78 3.77 324 564
Embodiment 9 3.22 711 679 3.79 3.77 326 528
Embodiment 10 3.27 710 681 3.78 3.78 327 601
Embodiment 11 3.27 703 674 3.78 3.79 325 617
Embodiment 12 3.2 700 670 3.75 3.72 320 612
Embodiment 13 3.21 700 672 3.75 3.73 321 620
Comparative example 1 2.99 708 648 3.77 3.68 318 180
Comparative example 2 3.05 709 651 3.92 3.8 317 320
Comparative example 3 2.96 707 659 3.86 3.73 315 410
Comparative example 4 3.17 705 643 3.83 3.75 318 266
Comparative example 5 2.88 705 658 3.84 3.75 317 253
Comparative example 6 3.14 706 644 3.83 3.75 319 211
Comparative example 7 2.98 703 682 4 3.81 309 430
From table 2, table 3 as can be known: the secondary cell of embodiment 1-13, active material density, energy density and charge and discharge circulation life are all than comparative example 1-7 height.
To this, only use the secondary cell of lithium/nickel/cobalt composite oxide as the comparative example 1 of positive active material, its charge and discharge circulation life is obviously short.The secondary cell of the comparative example 2 of the amount of the lithium/nickel/cobalt composite oxide in the positive active material below 50 weight %, and only use the secondary cell of lithium cobalt composite oxide as the comparative example 7 of active material, though the average working voltage height during discharge, charge and discharge circulation life is short.
(D C50/ D C10) and (D C90/ D C50) depart from the secondary cell and the (D of comparative example 3,4 of the scope of 1.4-2 N50/ D C50) departing from the secondary cell of comparative example 5,6 of the scope of 1.5-2.5, active material density, lC capacity, energy density and charge and discharge circulation life are all low than embodiment 1-13.
In the above-described embodiments, to having used by LiCoO 2Particle and LiNi 0.81Co 0.19O 2The example of the positive active material that 2 kind particles of particle constitute is illustrated, but as positive active material, as long as can improve charge and discharge circulation life, can also use at LiCoO 2Particle and LiNi 0.81Co 0.19O 2Mix as LiMn in the particle 2O 4The material that the particle by more than 3 kinds of the particle of other such kinds constitutes.
In the above-described embodiments, though the example that slim rechargeable nonaqueous electrolytic battery and prismatic nonaqueous electrolyte secondary battery was suitable for is illustrated, but the present invention is suitable for too to cylindrical shape rechargeable nonaqueous electrolytic battery, Coin shape rechargeable nonaqueous electrolytic battery.
The possibility of industrial utilization
Adopt aforesaid the present invention, a kind of rechargeable nonaqueous electrolytic battery that improves charge and discharge circulation life can be provided.

Claims (7)

1. rechargeable nonaqueous electrolytic battery, it comprises positive pole, negative pole and the nonaqueous electrolyte that contains positive active material, it is characterized in that, above-mentioned positive active material contains the oxide particle shown in oxide particle shown in the following formula A and the following formula B, oxide particle shown in the above-mentioned A in the above-mentioned positive active material surpasses 50 weight % with respect to the ratio of the total weight of the oxide particle shown in oxide particle shown in the above-mentioned formula A and the above-mentioned formula B, and above-mentioned positive active material satisfies following formula 1-5:
Li xNi yCo zM wO 2 A
Li aCo bM cO 2 B
Wherein M is the element more than a kind that is selected among Mn, B, Al and the Sn; Above-mentioned mol ratio x, y, z, w, a, b, c represent 0.95≤x≤1.05,0.7≤y≤0.95,0.05≤z≤0.3,0≤w≤0.1,0.95≤y+z+w≤1.05,0.95≤a≤1.05,0.95≤b≤1.05,0≤c≤0.05,0.95≤b+c≤1.05 respectively;
1.4≤(D N90/D N50)≤2 1
1.4≤(D N50/D N10)≤2 2
1.4≤(D C90/D C50)≤2 3
1.4≤(D C50/D C10)≤2 4
1.5≤(D N50/D C50)≤2.5 5
Above-mentioned D N10, D N50, D N90Expression Li xNi yCo zM wO 2The volume accumulation frequency of particle is 10%, 50%, 90% particle diameter; Above-mentioned D C10, D C50, D C90Expression Li aCo bM cO 2The particle diameter of the volume of particle accumulation frequency 10%, 50%, 90%, wherein volume accumulation frequency is that 10%, 50%, 90% particle diameter is meant, measures above-mentioned Li xNi yCo zM wO 2Particle and above-mentioned Li aCo bM cO 2The possessive volume of each particle that each comfortable granularity of particle is interregional, 10% o'clock the particle diameter that aforementioned possessive volume accumulation reaches whole distribution is decided to be the particle diameter of volume accumulation frequency 10%, 50% o'clock the particle diameter that aforementioned possessive volume accumulation reaches whole distribution is decided to be the particle diameter of volume accumulation frequency 50%, and 90% o'clock the particle diameter that aforementioned possessive volume accumulation reaches whole distribution is decided to be the particle diameter of volume accumulation frequency 90%.
2. rechargeable nonaqueous electrolytic battery according to claim 1 is characterized in that, above-mentioned Li aCo bM cO 2The above-mentioned D of particle C50In the scope of 0.2 μ m-30 μ m.
3. rechargeable nonaqueous electrolytic battery according to claim 1 is characterized in that, size ratio D N90/ D N50Satisfy 1.5≤D N90/ D N50≤ 1.9.
4. rechargeable nonaqueous electrolytic battery according to claim 1 is characterized in that, size ratio D N50/ D N10Satisfy 1.5≤D N50/ D N10≤ 1.9.
5. rechargeable nonaqueous electrolytic battery according to claim 1 is characterized in that, size ratio D C90/ D C50Satisfy 1.5≤D C90/ D C50≤ 1.9.
6. rechargeable nonaqueous electrolytic battery according to claim 1 is characterized in that, size ratio D C50/ D C10Satisfy 1.5≤D C50/ D C10≤ 1.9.
7. rechargeable nonaqueous electrolytic battery according to claim 1, it is characterized in that, the oxide particle shown in the above-mentioned A formula in the above-mentioned positive active material with respect to the ratio of the total weight of the oxide particle shown in oxide particle shown in the above-mentioned formula A and the above-mentioned formula B greater than 50 weight %, below 90 weight %.
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