CN100389512C - Nonaqueous electrolyte battery - Google Patents

Nonaqueous electrolyte battery Download PDF

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Publication number
CN100389512C
CN100389512C CNB2004800127859A CN200480012785A CN100389512C CN 100389512 C CN100389512 C CN 100389512C CN B2004800127859 A CNB2004800127859 A CN B2004800127859A CN 200480012785 A CN200480012785 A CN 200480012785A CN 100389512 C CN100389512 C CN 100389512C
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nonaqueous electrolyte
electrolyte battery
carbon
battery
carbonate
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CN1788370A (en
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中川裕江
稻益德雄
温田敏之
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GS Yuasa International Ltd
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Yuasa Battery Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/10—Energy storage using batteries

Abstract

A nonaqueous electrolyte battery excelling in battery performance in high-temperature environment. In particular, a nonaqueous electrolyte battery including a positive electrode and a negative electrode and, interposed therebetween, a nonaqueous electrolyte containing at least one cyclic carbonate having a carbon to carbon pi bond and at least one cyclic organic compound having an S=O bond, characterized in that the main component of positive electrode active substance as a constituent of the positive electrode is an oxide firing product of lamellar rock salt crystal structure represented by the formula Lim [NibM(1-b)O2] (wherein M represents at least one element of Groups 1 to 16 excluding Ni, Li and O, and 0 <= m <= 1.1) wherein the value of b satisfies the relationship 0 < b < 1, especially an oxide firing product of lamellar rock salt crystal structure represented by the formula Lim [MnaNibCocO2] (wherein 0 <= m <= 1.1, a+b+c = 1, ||a-b|| <= 0.05, a<>0 and b<>0) wherein the value of c satisfies the relationship 0 <= c < 1.

Description

Nonaqueous electrolyte battery
Technical field
The present invention relates to nonaqueous electrolyte battery, particularly relate to the nonaqueous electrolyte and the positive active material that are used for nonaqueous electrolyte battery.
Background technology
In recent years, preserve with power supply, electric vehicle power supply etc. with power supply, electric power as the e-machine that more and more moves towards high performance, miniaturization, the various nonaqueous electrolyte batteries of nonaqueous electrolyte that used that can obtain high-energy-density are concerned by people.
For nonaqueous electrolyte battery, generally be with lithium metal oxide as anodal, as negative pole, the nonaqueous electrolyte that will dissolve lithium salts in the organic solvent is as electrolyte with the material with carbon element of lithium metal or lithium alloy, adsorbable release lithium ion.Particularly, lithium hexafluoro phosphate (LiPF 6) to wait the nonaqueous electrolyte of electrolyte dissolution in the nonaqueous solvents that with the ethylene carbonate is the main composition composition be to be familiar with for people.
In addition, the known lithium metal oxide as positive active material has LiCoO 2, LiNiO 2, LiMnO 2, LiMn 2O 4Composite oxides Deng lithium and transition metal.Especially, can expect the α-NaFeO that has of high-energy-density 2In the positive active material of structure, with LiCoO 2Deng just being widely used for the lithium cobalt composite oxide of representative.
One of desired performance of this nonaqueous electrolyte battery is the charge-discharge performance under the hot environment.That is, e-machine is to use under hot environment with the power supply most cases, the problem that exists battery performance to reduce easily in this case.Particularly, not only there is the problem of environment for use temperature in the electric power storage with power supply, electric vehicle power supply etc., and also serious by the maximize accumulation of heat problem produced of battery, even so strong request under hot environment, discharge and recharge, performance reduces also few nonaqueous electrolyte battery.
Therewith correspondingly, as nonaqueous electrolyte battery, in patent documentation 1 (spy opens flat 11-67266 communique), put down in writing positive pole has been used LiCoO with good battery performance 2Perhaps LiMn 2O 4, and use contains the battery of the nonaqueous electrolyte of propylene carbonate, linear carbonate and vinylene carbonate.In patent documentation 2 (spy opens flat 11-162511 communique), put down in writing positive pole has been used LiCoO 2, use has the battery of the solvent of S=O key to nonaqueous electrolyte.In patent documentation 3 (spy opens the 2002-83632 communique), put down in writing positive pole has been used LiCoO 2, nonaqueous electrolyte is used propylene carbonate, 1, the battery of 3-propane sultone and vinylene carbonate.
But, have the not necessarily sufficient problem of charge-discharge performance under the hot environment.
Summary of the invention
The present invention carries out in view of the above problems, and its problem provides the nonaqueous electrolyte battery of the battery performance excellence under the hot environment.
In order to solve above-mentioned problem, the inventor finds that by making the nonaqueous solvents that constitutes nonaqueous electrolyte be specific material, and uses the positive active material of specific composition through concentrating on studies, can solve above-mentioned problem.That is, technology formation of the present invention and action effect thereof are as described below.Just, the relevant mechanism of action has comprised the supposition part, and its correctness does not limit the present invention.
(1) the present invention relates to a kind of nonaqueous electrolyte battery, it is characterized in that, have positive pole and negative pole, by using the nonaqueous electrolyte contain the cyclic carbonate with carbon-to-carbon π key more than a kind or a kind respectively and to have the cyclic organic compounds of S=O key to make, and the principal component of positive active material that constitutes described positive pole is for using Li m[Ni bM (1-b)O 2] expression the oxide sintered body with stratiform rock salt type crystal structure, wherein, M is the element of 1～16 family more than a kind or a kind except Ni, Li and O, 0≤m≤1.1, the value of described b is 0＜b＜1.
At this, be used to make and conceptively between above-mentioned " the cyclic carbonate " and above-mentioned " cyclic organic compounds " of formation nonaqueous electrolyte battery of battery of the present invention do not repeat with S=O key with carbon-to-carbon π key.That is, above-mentioned " cyclic carbonate with carbon-to-carbon π key " do not have the S=O key.
(2) above-mentioned (1) described nonaqueous electrolyte battery is characterized in that, the value of described b is 0.08≤b≤0.55.
(3) above-mentioned (2) described nonaqueous electrolyte battery is characterized in that, the value of described b is 0.25≤b≤0.55.
(4) any described nonaqueous electrolyte battery of above-mentioned (1)～(3) is characterized in that, described M is Mn or Mn and Co.
(5) above-mentioned (4) described nonaqueous electrolyte battery is characterized in that, described oxide sintered body is for using Li m[Mn aNi bCo cO 2] expression the oxide sintered body with stratiform rock salt type crystal structure, wherein, 0≤m≤1.1, a+b+c=1, | a-b|≤0.05, a ≠ 0, b ≠ 0, the value of described c is 0≤c＜1.
(6) above-mentioned (5) described nonaqueous electrolyte battery is characterized in that, the value of described c is 0＜c≤0.84.
(7) above-mentioned (6) described nonaqueous electrolyte battery is characterized in that, the value of described c is 0＜c≤0.5.
(8) any described nonaqueous electrolyte battery of above-mentioned (1)～(7) is characterized in that, the cyclic organic compounds of the described S=O of having key has any one the represented structure with Chemical formula 1～chemical formula 4.
Figure C20048001278500061
(Chemical formula 1)
Figure C20048001278500062
(Chemical formula 2)
Figure C20048001278500063
(chemical formula 3)
Figure C20048001278500064
(chemical formula 4)
(9) above-mentioned (8) described nonaqueous electrolyte battery, it is characterized in that, the cyclic organic compounds of the described S=O of having key is for being selected from glycol sulfite, the inferior propyl ester of sulfurous acid, sulfolane, ring cyclobufene sultone, 1,3-propane sultone, 1, at least a in 4-butane sultone and their derivative.
(10) any described nonaqueous electrolyte battery of above-mentioned (1)～(9), it is characterized in that, described cyclic carbonate with carbon-to-carbon π key is for being selected from vinylene carbonate, carbonic acid benzene ethyl, catechol carbonic ester, vinylethylene carbonate, carbonic acid-1-phenyl vinylene, carbonic acid-1, at least a in the 2-diphenyl vinylene.
(11) any described nonaqueous electrolyte battery of above-mentioned (1)～(10) is characterized in that described nonaqueous electrolyte contains the cyclic carbonate with carbon-to-carbon π key.
(12) above-mentioned (11) described nonaqueous electrolyte battery is characterized in that, the described cyclic carbonate that does not have carbon-to-carbon π key is to be selected from least a in ethylene carbonate, propylene carbonate, the butylene carbonate.
(13) any described nonaqueous electrolyte battery of above-mentioned (1)～(12) is characterized in that the principal component that constitutes the negative electrode active material of described negative pole is a graphite.
According to the present invention, can be provided in the nonaqueous electrolyte battery of the battery performance excellence under the hot environment.
Description of drawings
Fig. 1 is the sectional view of the nonaqueous electrolyte battery that uses among the embodiment;
Fig. 2 is the figure of the high temperature charge-discharge performance of expression battery of the present invention and comparison battery;
Fig. 3 is the figure of the high temperature charge-discharge performance of expression battery of the present invention and comparison battery.
Symbol description
1 positive pole
11 anode mixtures
12 positive electrode collectors
2 negative poles
21 cathode agents
22 negative electrode collectors
3 dividing plates
4 utmost point groups
5 metal-resin composite membranes
Embodiment
For the oxide sintered body as positive active material of the present invention, general expression Li m[Ni bM (1- B)O 2] in, M is the element of 1～16 family more than a kind or a kind except Ni, Li and O, be preferably can with the element of Ni displacement.Can enumerate for example Be, B, V, C, Si, P, Sc, Cu, Zn, Ga, Ge, As, Se, Sr, Mo, Pd, Ag, Cd, In, Sn, Sb, Te, Ba, Ta, W, Pb, Bi, Co, Fe, Cr, Mn, Ti, Zr, Nb, Y, Al, Na, K, Mg, Ca, Cs, La, Ce, Nd, Sm, Eu, Tb etc., but be not limited to these elements.These elements can be used alone, but also also mix together more than 2 kinds or 2 kinds.Especially, when M selects, can obtain the significant especially effect of deep discharge performance from V, Al, Mg, Mn, Co, Cr, Ti, therefore more preferred.
Especially as described later employed such among the embodiment, when using Mn or Mn and Co to constitute above-mentioned M, can bring into play the favorable charge-discharge cycle performance as essential element, be preferred therefore.At this moment, the atomic ratio of further preferred Mn and Ni is 1: 1.Thereby, consider the error in the manufacturing of oxide sintered body, Li m[Mn aNi bCo cO 2] composition represent to be preferably | a-b|≤0.05.
When adding element such as a small amount of Al, In and Sn as M, the stability of crystal structure can increase, and is preferred therefore.At this moment, at [Ni bM (1-b)O 2] in the ratio of element such as shared above-mentioned Al, In and Sn be preferably smaller or equal to 0.1.
As the method that imports element M at the synthesis phase of oxide sintered body, can enumerate the method for adding substitutional element in the raw material in advance, burn till LiNiO burning till of active material 2The method of back by displacement such as ion-exchange heterogeneous element etc., but be not limited to these methods.
The total content that has the carbonic ester of carbon-to-carbon π key and have a cyclic organic compounds of S=O key is preferably 0.01 weight %～20 weight % with respect to the total weight of nonaqueous electrolyte, more preferably 0.10 weight %～10 weight %.The carbonic ester by having carbon-to-carbon π key and the total content of cyclic organic compounds with S=O key with respect to the total weight of nonaqueous electrolyte for more than or equal to 0.01 weight %, substantially fully constitute the decomposition of other organic solvents of nonaqueous electrolyte in the time of can being suppressed at initial charge, can more positively charge.In addition, by being controlled at smaller or equal to 20 weight %, carbonic ester with carbon-to-carbon π key that contains because of surplus or the cyclic organic compounds with S=O key are decomposed the battery performance that causes on positive pole deterioration can take place hardly, can bring into play sufficient battery performance.Carbonic ester with carbon-to-carbon π key can at random be selected with the content ratio with cyclic organic compounds of S=O key, but preferred weight ratio is about 1: 1.
The organic solvent that constitutes nonaqueous electrolyte can use and be normally used for the organic solvent of nonaqueous electrolyte battery with nonaqueous electrolyte.Can enumerate for example cyclic carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, carbonic acid chlorine ethyl; Cyclic esters such as gamma-butyrolacton, gamma-valerolactone, propiolactone; Linear carbonate such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, diphenyl carbonate; Chain such as methyl acetate, methyl butyrate ester; Oxolane or derivatives thereof, 1, ethers such as 3-diox, dimethoxy-ethane, diethoxyethane, methoxy ethoxy ethane, diethylene glycol dimethyl ether; 1 kind of nitrile such as acetonitrile, benzonitrile etc., the mixture more than 2 kinds or 2 kinds etc.But be not limited to these.In addition, also can use the anti-flammability solvent phosphate that adds to usually in the nonaqueous electrolyte battery usefulness electrolyte.Can enumerate for example trimethyl phosphate, triethyl phosphate, ethyl dimethyl phosphate, diethylmethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate, tricresyl phosphate (trifluoro methyl esters), tricresyl phosphate (trifluoro ethyl ester) etc., but be not limited to these.These phosphates can be used alone, but also also mix together more than 2 kinds or 2 kinds.
In addition, in the present invention, by further contain the cyclic carbonate that does not have carbon-to-carbon π key with high-k in nonaqueous electrolyte, can bring into play effect of the present invention fully, be preferred therefore.At this, the above-mentioned cyclic carbonate that does not have a carbon-to-carbon π key preferably from boiling point more than or equal to selecting 240 ℃ the carbonic ester.Wherein, especially preferably contain and be selected from least a in the group of forming by ethylene carbonate, propylene carbonate and butylene carbonate.At this, the above-mentioned cyclic carbonate shared ratio in nonaqueous electrolyte that does not have carbon-to-carbon π key is preferably more than and equals 30 volume %.
As the lithium salts that constitutes nonaqueous electrolyte without any restriction, can use the lithium salts that is normally used for nonaqueous electrolyte battery at wide current potential regional stability.Can enumerate for example LiBF 4, LiPF 6, LiClO 4, LiCF 3SO 3, LiN (CF 3SO 2) 2, LiN (C 2F 5SO 2) 2, LiN (CF 3SO 2) (C 4F 9SO 2), LiC (CF 3SO 2) 3, LiC (C 2F 5SO 2) 3Deng, but be not limited to these.These lithium salts can be used alone, but also also mix together more than 2 kinds or 2 kinds.Mix and use LiPF 6Or LiBF 4Deng inorganic lithium salt and LiN (CF 3SO 2) 2Or LiN (C 2F 5SO 2) 2When having the organic lithium salt of perfluoroalkyl, have the effect that improves the high temperature retention, therefore more preferred.
In order positively to obtain having the nonaqueous electrolyte battery of high battery behavior, the concentration of the lithium salts in the nonaqueous electrolyte is preferably 0.1mol/l～5mol/l, more preferably 1mol/l～2.5mol/l.
As the negative electrode active material of the main composition composition of negative pole, can enumerate metal oxides such as material with carbon element, tin-oxide, Si oxide, also have in order to improve the negative pole characteristic and in these materials, add the material etc. that phosphorus or boron carry out modification.Graphite in the material with carbon element is owing to have extremely operating potential near lithium metal, and therefore self discharge is few when adopting lithium salts as electrolytic salt, and the irreversible capacity when discharging and recharging is also few, thereby is preferred as negative electrode active material.And then, in the present invention because use contains cyclic carbonate with carbon-to-carbon π key and the nonaqueous electrolyte with cyclic organic compounds of S=O key, therefore when charging, on the negative pole that with graphite is principal component, can positively suppress to constitute the decomposition of other organic solvents of nonaqueous electrolytic solution, can positively embody the above-mentioned advantageous feature of graphite.
Below the expression graphite that can suit to adopt is according to the analysis result of X-ray diffraction etc.:
Lattice plane is (d002) 0.333～0.350nm at interval
The big or small La of the axial crystallite of a is more than or equal to 20nm
The big or small Lc of the axial crystallite of c is more than or equal to 20nm
Real density 2.00～2.25g/cm 3
In addition, also can in graphite, add metal oxides such as tin-oxide, Si oxide, phosphorus, boron, amorphous carbon etc. and carry out modification.Particularly, can suppress the decomposition of electrolyte, improve battery behavior by surface with the said method modified graphite, from but preferred.And then, by inserting graphite behind the lithium etc. and also can be used as negative electrode active material to graphite and with alloy etc. or prior reduction that lithium metal, lithium-aluminium, lithium-lead, lithium-Xi, lithium-aluminium-Xi, lithium-gallium and Wood's metal etc. contain the lithium metal with electrochemical means.
In positive pole and the negative pole, except above-mentioned active material, can use conductive agent, binding agent, collector body well known in the art according to known method as required as the main composition composition.
As conductive agent, so long as can not produce dysgenic electronic conductivity material to battery behavior, just without limits, can contain a kind or their mixture of conductive materials such as native graphite (flaky graphite, flaky graphite, amorphous graphite etc.), Delanium, carbon black, acetylene black, Ketjen black (Ketjen black), carbon whisker, carbon fiber, metal (copper, nickel, aluminium, silver, gold etc.) powder, metallic fiber, conductivity ceramic material usually.
In these conductive agents, consider preferred acetylene black from the angle of conductivity and coating.The addition of conductive agent is preferably 1～50 weight % with respect to the total weight of positive pole or negative pole, is preferably 2 weight %～30 weight % especially.The mixed method of these conductive agents is physical mixed, and desirable state is to mix equably.For this reason, can carry out dry type or wet mixed with powder mixers such as V-Mixer, S type mixer, grinder, ball mill, planetary ball mills.
In addition, also can or have the powder of compound-modified positive active material of hydrophobic grouping and the surface layer part at least of the powder of negative electrode active material with the good material of electronic conductivity or ionic conductivity.For example can enumerate by using technology such as plating, sintering, mechanical fusion, evaporation, burning be attached and cover the good materials of electronic conductivity such as gold, silver, carbon, nickel, copper, or good material of lithium carbonate, boron glass, solid electrolyte plasma conductibility or silicone oil etc. have the material of hydrophobic grouping.
The powder of positive active material and the preferred average particle size of the powder of negative electrode active material are smaller or equal to 100 μ m.In order to improve the high output characteristic of nonaqueous electrolyte battery, the powder of positive active material especially is preferably smaller or equal to 10 μ m.In order to obtain the powder of regulation shape, can use pulverizer and grader.Can use for example mortar, ball mill, sand mill, vibrator, planetary ball mill, injector-type mill, retro jet formula grinding machine, swirling eddy type injector-type mill or sieve etc.Also can adopt coexistence that the case of wet attrition of organic solvents such as water or hexane is arranged during pulverizing.Do not have special restriction as stage division, dry type, wet type all can be used sieve and air classifier etc. as required.
As binding agent, usually can use thermoplastic resins such as polytetrafluoroethylene, Kynoar, polyethylene, polypropylene, ethylene propylene diene rubber (EPDM), sulfone EPDM, butadiene-styrene rubber (SBR), fluorubber etc. have the polymer of caoutchouc elasticity, the mixture more than a kind or 2 kinds or 2 kinds of polysaccharides such as carboxymethyl cellulose etc.In addition, when this binding agent that has with the functional group of lithium reaction of polysaccharide was used for lithium battery, processing such as preferably for example methylate in advance made its functional group's inactivation.The addition of binding agent is preferably 1～50 weight % with respect to the total weight of positive pole or negative pole, is preferably 2～30 weight % especially.
By in organic solvent such as toluene or water, adding positive active material or negative electrode active material, conductive agent and binding agent and mixing, reshape to electrode shape and carry out drying, can make positive pole and negative pole aptly respectively.
In addition, be preferably formed for positive pole adhere to anodal with on the collector body, negative pole adheres to negative pole with structure such on the collector body.For example as the anodal collector body of using, except aluminium, titanium, stainless steel, nickel, burn till carbon, electroconductive polymer, the conductive glass etc., in order to improve caking property, conductivity and oxidative resistance, can also use the material of using after carbon, nickel, titanium or silver etc. are handled the surface of aluminium or copper etc.As the negative pole collector body, except copper, nickel, iron, stainless steel, titanium, aluminium, burn till carbon, electroconductive polymer, conductive glass, the Al-Cd alloy etc., in order to improve caking property, conductivity and oxidative resistance, can also use with carbon, nickel, titanium or silver etc. and handle material behind the surface of copper etc.Also can carry out surface oxidation treatment at these materials.
At the shape of collector body, except the paper tinsel shape, can also use membranaceous, sheet, netted, by organizator of the object of punching or expansion, lath body, porous body, foaming body, groups of fibers etc.Thickness does not have special restriction, can use the thickness of 1～500 μ m.In these collector bodies, preferably use the aluminium foil of oxidative resistance excellence as positive pole with collector body, preferably use in reduction stable and excellent electric conductivity, cheap Copper Foil, nickel foil, iron foil with collector body and contain the Alloy Foil of these materials of part as negative pole.And then, being preferably the paper tinsel of matsurface surface roughness more than or equal to 0.2 μ mRa, the caking property of positive pole and negative pole and collector body can become excellent thus.Thereby, consider from aspect with such matsurface, preferably use the electrolysis paper tinsel.Particularly, most preferably implemented the electrolysis paper tinsel that annular knurl is handled.
Dividing plate as nonaqueous electrolyte battery can use micro-porous film well known in the art or nonwoven fabrics etc. according to known method.When using polymer solid electrolyte or gel electrolyte, can have the function of aforementioned barriers concurrently as nonaqueous electrolyte.In addition, also the dividing plate of polymer solid electrolyte or gel electrolyte and above-mentioned micro-porous film or nonwoven fabrics etc. can be used simultaneously.
Preferred separately or and with micro-porous film that demonstrates excellent speed characteristic and nonwoven fabrics etc. as nonaqueous electrolyte battery with dividing plate.As constituting the material of nonaqueous electrolyte battery with dividing plate, can enumerate for example with polyethylene, polypropylene etc. are the vistanex of representative, with PETG, polybutylene terephthalate (PBT)s etc. are the mylar of representative, Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene-perfluorovinyl sulfide ether copolymer, vinylidene-TFE copolymer, vinylidene-trifluoro-ethylene copolymer, vinylidene-fluoride copolymers, vinylidene-Hexafluoro acetone copolymer, vinylidene-ethylene copolymer, vinylidene-propylene copolymer, vinylidene-trifluoro propene copolymer, vinylidene-tetrafluoraoethylene-hexafluoropropylene copolymer, vinylidene-ethylene-tetrafluoroethylene copolymer etc.
Consider that from the angle of intensity nonaqueous electrolyte battery is preferably smaller or equal to 98 volume % with the void content of dividing plate.And, consider that from the angle of charge-discharge characteristic void content is preferably more than and equals 20 volume %.
In addition, nonaqueous electrolyte battery also can use the polymer gel that is made of polymer such as for example acrylonitrile, oxirane, expoxy propane, methyl methacrylate, vinylacetate, vinyl pyrrolidone, Kynoar and electrolyte with dividing plate.
And then, for the nonaqueous electrolyte battery dividing plate, when aforesaid perforated membrane or nonwoven fabrics etc. are used jointly with polymer gel, can improve guarantor's fluidity of electrolyte, be preferred therefore.That is, be formed on that cladding thickness keeps electrolyte, thereby makes above-mentioned solvophilic polymer gelization smaller or equal to the film of several microns solvophilic polymer on the surface of polyethene microporous membrane and the micropore wall in the micropore of this film.
As this solvophilic polymer, except Kynoar, also can enumerate polymer after crosslinked such as acrylate monomer, the epoxy monomer with Oxyranyle or ester group etc., monomer etc. with NCO.When crosslinked, can use heat, ultraviolet ray (UV) and electron ray (EB) isoreactivity light etc.
By for example before the lamination nonaqueous electrolyte battery is with dividing plate, positive pole and negative pole or after the lamination, injecting electrolyte, with the housing material sealing, can make the nonaqueous electrolyte battery that the present invention relates to aptly at last.In addition, reel anodal and negative pole accompany nonaqueous electrolyte battery with dividing plate by the formed nonaqueous electrolyte battery of the generating element of lamination in, electrolyte preferably is injected into generating element in above-mentioned coiling front and back.As electrolyte filling method, can under normal pressure, carry out fluid injection, also can use vacuum infiltration method and pressurization osmosis.
Can use metal can well known in the art and metal resin composite material etc. according to known method as housing material.Consider preferred thin material, for example preferred metal resin composite material that clips this structure of metal forming with resin molding from the light-weighted angle of nonaqueous electrolyte battery.As the object lesson of metal forming, so long as aluminium, iron, nickel, copper, stainless steel, titanium, gold, silver etc. do not have the paper tinsel of pin hole, just without limits, the aluminium foil that preferred mass is light and cheap.In addition, as the resin molding of transmitted intensity excellences such as the preferred PETG film of the resin molding of outside batteries side, nylon membrane, the film that can hot melt applies and have solvent resistance as the resin molding preferably polyethylene film of inside battery side, nylon membrane etc.
Illustrate in greater detail the present invention by the following examples, but the present invention is not limited to these descriptions.
Embodiment 1
At first, the manufacture method at the oxide sintered body with stratiform rock salt type crystal structure of the battery that is used for present embodiment illustrates and obtains LiMn 0.42Ni 0.42Co 0.16O 2Method for compositions.
In the hermetic type reactive tank, add 3.5 premium on currency.And then add 32% sodium hydrate aqueous solution, make pH=11.6.The mixer that use has an oar formula stirring vane stirs with the rotating speed of 1200rpm, by external heater solution temperature in the reactive tank is remained on 50 ℃.In addition, the solution in above-mentioned reactive tank blows argon gas, removes the dissolved oxygen in the solution.
On the other hand, modulation is as the aqueous solution that is dissolved with transition metal of material solution.Mix the manganese sulfate pentahydrate aqueous solution, the nickel sulfate hexahydrate compound aqueous solution, the cobaltous sulfate heptahydrate aqueous solution and the hydrazine monohydrate aqueous solution, and make that manganese concentration is that 0.738mol/l, nickel concentration are that 0.738mol/l, cobalt concentration are that 0.282mol/l and hydrazine concentration are that 0.0101mol/l obtains.
Flow with 3.17ml/min drips this material solution to above-mentioned reactive tank continuously.Simultaneously, the flow with 0.22ml/min drips the ammonia solution of 12mol/l to mix.And add 32% sodium hydrate aqueous solution intermittently, making the pH of solution in the above-mentioned reactive tank constant is 11.4 ± 0.1.With heater control, make the solution temperature in the above-mentioned reactive tank constant intermittently at 50 ℃.Directly blow argon gas in solution, making in the above-mentioned reactive tank becomes reducing atmosphere.And use the stream pump to efflux out slurries to system, make solution amount be always 3.5 liters quantitatively.Begin through after 60 hours from reaction, in 5 hours from the slurries of bottom sampling as the Ni-Mn-Co composite oxides of reactive crystallization thing.The slurries of washing, sampling by filtration 80 ℃ of one evenings of drying, obtain the dried powder of Ni-Mn-Co co-precipitation presoma.
The Ni-Mn-Co co-precipitation precursor powder that obtains is sized to less than 75 μ m, and weighing lithium hydroxide one water salt powder makes Li/ (Ni+Mn+Co)=1.0, mixes with planetary milling device again.It is filled in the oxidation aluminum mortar, uses electric furnace programming rate with 100 ℃/hr under the dry air circulation to be warming up to 850 ℃, keeps 850 ℃ temperature 15hr, follow, be cooled to 200 ℃ with the cooling rate of 100 ℃/hr, subsequently natural cooling.Be sized to smaller or equal to 75 μ m by the powder that will obtain, obtain the powder of lithium nickel manganese cobalt composite oxide.The powder that the results verification that X-ray diffraction is measured obtains is the single phase with stratiform rock salt type crystal structure.The results verification that ICP measures consists of LiNi 0.42Mn 0.42Co 0.16O 2
In addition, following various compositions that are used for battery of the present invention and comparison battery uses Li m[Mn aNi bCo cO 2] the oxide sintered body with stratiform rock salt type crystal structure of expression, the mole of transistion metal compound that is used to make above-mentioned raw materials solution by adjusting is recently synthetic.
The sectional view of the nonaqueous electrolyte battery that is used for present embodiment is shown in Table 1.Nonaqueous electrolyte battery in the present embodiment is made of utmost point group 4, nonaqueous electrolyte and metal-resin composite membrane 5, and described utmost point group 4 comprises positive pole 1, negative pole 2 and dividing plate 3.Positive pole 1 forms by coating anode mixture 11 on positive electrode collector 12.Negative pole 2 forms by coating cathode agent 21 on negative electrode collector 22.Nonaqueous electrolyte is soaked in utmost point group 4.Metal-resin composite membrane 5 covers utmost point group 4, applies sealed by hot melt around it.
The manufacture method of the nonaqueous electrolyte battery of the above-mentioned formation that is used for present embodiment then, is described.
Anodal 1 following obtaining.At first, mixed cathode active material and as the acetylene black of conductive agent, and then mixing is as the N-N-methyl-2-2-pyrrolidone N-solution of the Kynoar of binding agent, this mixture is coated on the face of the positive electrode collector 12 that is formed by aluminium foil, carry out drying then, the thickness that is pressed into anode mixture 11 is 0.1mm.Obtain anodal 1 by above operation.
Negative pole 2 following obtaining.At first, mixing is as the graphite of negative electrode active material with as the N-N-methyl-2-2-pyrrolidone N-solution of the Kynoar of binding agent, this mixture is coated on the face of the negative electrode collector 22 that is formed by Copper Foil, carries out drying then, the thickness that is pressed into cathode agent 21 is 0.1mm.Obtain negative pole 2 by above operation.
Dividing plate 3 following obtaining.At first, making is dissolved with the ethanolic solution of two functional acrylate's monomers of the structure that having of 3 weight % represent with chemical formula 5, and (average pore size is that 0.1 μ m, percent opening are 50%, thickness is that 23 μ m, weight are 12.52g/cm to be applied to the porous substrate polyethene microporous membrane 2, air permeability be 89 seconds/100ml) go up after, make monomer crosslinkedly by the electron ray irradiation, form organic polymer layers, 60 ℃ of dryings of temperature 5 minutes.By above operation, obtain dividing plate 3.Here, the thickness of resultant dividing plate 3 is 24 μ m, and weight is 13.04g/cm 2, air permeability is 103 seconds/100ml, and the weight of organic polymer layers is about 4 weight % with respect to the weight of porous material, and the thickness of crosslinked body layer is about 1 μ m, and former state is roughly kept in the hole of porous substrate.
Figure C20048001278500151
(chemical formula 5)
Utmost point group 4 disposes dividing plate 3 betwixt by making anode mixture 11 and cathode agent 21 opposed, successively lamination positive pole 1, dividing plate 3, negative pole 2 and constitute.
Then, by utmost point group 4 is immersed in the nonaqueous electrolyte, utmost point group 4 is soaked into nonaqueous electrolyte.And then, cover utmost point group 4 with metal-resin composite membrane 5, apply sealed by hot melt around it.
With volume ratio is 6: 2: 2 mixed ethylene carbonate, propylene carbonate and diethyl carbonate, the LiPF of 1 mole of dissolving in 1 liter of this mixed solvent 6, and then mix 2 weight % vinylene carbonate, 2 weight % 1,3-propane sultone and obtain nonaqueous electrolyte uses this nonaqueous electrolyte, and use by X-ray diffraction measure the single phase of confirming as stratiform rock salt type crystal structure by LiMn 0.5Ni 0.5O 2The oxide sintered body that composition formula is represented obtains the nonaqueous electrolyte battery that design capacity is 100mAh as positive active material by above-mentioned manufacture method.With it as battery 1 of the present invention.
Embodiment 2
Use with embodiment 1 in the same nonaqueous electrolyte that uses, and use by X-ray diffraction measure the single phase of confirming as stratiform rock salt type crystal structure by LiMn 0.42Ni 0.42Co 0.16O 2The oxide sintered body that composition formula is represented obtains the nonaqueous electrolyte battery that design capacity is 100mAh as positive active material by above-mentioned manufacture method.With it as battery 2 of the present invention.
Embodiment 3
With volume ratio is 6: 2: 2 mixed ethylene carbonate, propylene carbonate and diethyl carbonate, the LiPF of 1 mole of dissolving in 1 liter of this mixed solvent 6, and then mix 2 weight % catechol carbonic ester, 2 weight % sulfolane and obtain nonaqueous electrolyte, use this nonaqueous electrolyte, and use by X-ray diffraction measure the single phase of confirming as stratiform rock salt type crystal structure by LiMn 0.33Ni 0.33Co 0.34O 2The oxide sintered body that composition formula is represented obtains the nonaqueous electrolyte battery that design capacity is 100mAh as positive active material by above-mentioned manufacture method.With it as battery 3 of the present invention.
Embodiment 4
With volume ratio is 6: 2: 2 mixed ethylene carbonate, propylene carbonate and diethyl carbonate, the LiPF of 1 mole of dissolving in 1 liter of this mixed solvent 6, and then mix 2 weight % vinylene carbonate, 2 weight % 1,4-butane sultone and obtain nonaqueous electrolyte uses this nonaqueous electrolyte, and use by X-ray diffraction measure the single phase of confirming as stratiform rock salt type crystal structure by LiMn 0.25Ni 0.25Co 0.5O 2The oxide sintered body that composition formula is represented obtains the nonaqueous electrolyte battery that design capacity is 100mAh as positive active material by above-mentioned manufacture method.With it as battery 4 of the present invention.
Comparative example 1
The same nonaqueous electrolyte that uses among use and the embodiment 1, and with LiCoO 2Be used for positive active material, obtain the nonaqueous electrolyte battery that design capacity is 100mAh by above-mentioned manufacture method.With its battery 1 as a comparison.
Embodiment 5
Use with embodiment 1 in the same nonaqueous electrolyte that uses, and use by X-ray diffraction measure the single phase of confirming as stratiform rock salt type crystal structure by LiMn 0.17Ni 0.17Co 0.67O 2The oxide sintered body that composition formula is represented obtains the nonaqueous electrolyte battery that design capacity is 100mAh as positive active material by above-mentioned manufacture method.With it as battery 5 of the present invention.
Embodiment 6
Use with embodiment 1 in the same nonaqueous electrolyte that uses, and use by X-ray diffraction measure the single phase of confirming as stratiform rock salt type crystal structure by LiMn 0.08Ni 0.08Co 0.84O 2The oxide sintered body that composition formula is represented obtains the nonaqueous electrolyte battery that design capacity is 100mAh as positive active material by above-mentioned manufacture method.With it as battery 6 of the present invention.
Embodiment 7
Use with embodiment 1 in the same nonaqueous electrolyte that uses, and use by X-ray diffraction measure the single phase of confirming as stratiform rock salt type crystal structure by LiMn 0.05Ni 0.05Co 0.9O 2The oxide sintered body that composition formula is represented obtains the nonaqueous electrolyte battery that design capacity is 100mAh as positive active material by above-mentioned manufacture method.With it as battery 7 of the present invention.
Embodiment 8
With volume ratio is 6: 2: 2 mixed ethylene carbonate, propylene carbonate and diethyl carbonate, the LiPF of 1 mole of dissolving in 1 liter of this mixed solvent 6, and then mix 2 weight % vinylethylene carbonate, 2 weight % glycol sulfite and obtain nonaqueous electrolyte, use this nonaqueous electrolyte, and use by X-ray diffraction measure the single phase of confirming as stratiform rock salt type crystal structure by LiMn 0.30Ni 0.55Co 0.15O 2The oxide sintered body that composition formula is represented obtains the nonaqueous electrolyte battery that design capacity is 100mAh as positive active material by above-mentioned manufacture method.With it as battery 8 of the present invention.
Comparative example 2
With volume ratio is 6: 2: 2 mixed ethylene carbonate, propylene carbonate and diethyl carbonate, the LiPF of 1 mole of dissolving in 1 liter of this mixed solvent 6And then mix the vinylene carbonate of 2 weight % and obtain nonaqueous electrolyte, use this nonaqueous electrolyte, and will be used as positive active material, obtain the nonaqueous electrolyte battery that design capacity is 100mAh by above-mentioned manufacture method with the same oxide sintered body of use among the embodiment 2.With its battery 2 as a comparison.
Comparative example 3
The same nonaqueous electrolyte that uses in use and the comparative example 2, and will be used as positive active material with the same oxide sintered body of use among the embodiment 3, obtain the nonaqueous electrolyte battery that design capacity is 100mAh by above-mentioned manufacture method.With its battery 3 as a comparison.
Comparative example 4
The same nonaqueous electrolyte that uses in use and the comparative example 2, and will be used as positive active material with the same oxide sintered body of use among the embodiment 4, obtain the nonaqueous electrolyte battery that design capacity is 100mAh by above-mentioned manufacture method.With its battery 4 as a comparison.
Comparative example 5
The same nonaqueous electrolyte that uses in use and the comparative example 2, and with LiCoO 2As positive active material, obtain the nonaqueous electrolyte battery that design capacity is 100mAh by above-mentioned manufacture method.With its battery 5 as a comparison.
Comparative example 6
The same nonaqueous electrolyte that uses in use and the comparative example 2, and will be used as positive active material with the same oxide sintered body of use among the embodiment 5, obtain the nonaqueous electrolyte battery that design capacity is 100mAh by above-mentioned manufacture method.With its battery 6 as a comparison.
Comparative example 7
The same nonaqueous electrolyte that uses in use and the comparative example 2, and will be used as positive active material with the same oxide sintered body of use among the embodiment 6, obtain the nonaqueous electrolyte battery that design capacity is 100mAh by above-mentioned manufacture method.With its battery 7 as a comparison.
Initial stage discharges and recharges test
Discharge and recharge test at battery 1～8 of the present invention and comparison 1～7 initial stage of carrying out of battery.That is, carrying out electric current at 20 ℃ is that 20mA, final voltage are the constant-current constant-voltage charging of 4.2V, obtains the initial stage charging capacity.Then, carrying out electric current at 20 ℃ is that 20mA, final voltage are the constant-current discharge of 2.7V, obtains the initial stage discharge capacity.The ratio (percentage) of above-mentioned initial stage discharge capacity and design capacity (100mAh) is set at " initial stage discharge capacity (%) ".
In addition, the ratio (percentage) with above-mentioned initial stage discharge capacity and initial stage charging capacity is set at " initial stage efficient (%) ".
The test of high temperature charge-discharge performance
Then, under being 50 ℃ hot environment, temperature carries out the charge and discharge cycles test.Charge condition and the discharging condition of this moment are same as described above.The discharge capacity that will circulate from the 200th time that above-mentioned initial stage discharge begins to count and the ratio (percentage) of above-mentioned initial stage discharge capacity are set at " high temperature charge-discharge performance (%) ".
High temperature is preserved test
Use the battery of making separately of the present invention 1～8 and compare battery 1～7, carry out high temperature and preserve test.At first, carry out the above-mentioned initial stage to discharge and recharge test, confirm the initial stage discharge capacity after, again to charge, under being 60 ℃ environment, temperature preserved 30 days then, behind the battery recovery to 20 ℃ with above-mentioned same condition, with above-mentioned same condition under discharge, obtain self-discharge rate.Here, self-discharge rate is that through type 1 calculates.
(formula 1)
Figure C20048001278500181
Above battery testing be the results are shown in table 1 and the table 2.
Table 1
There is cyclic organic compounds with S=O key General expression Li m[Mn aNi bCo cO 2] in the value of c General expression Li m[Ni bM (1-b)O 2] in the value of b Initial stage discharge capacity (%) Initial stage efficient (%) High temperature charge-discharge performance (%) High temperature is preserved back self-discharge rate (%)
Embodiment 1 0 0.5 96 80 80 16
Embodiment 2 0.16 0.42 97 85 87 10
Embodiment 3 0.34 0.33 98 88 82 15
Embodiment 4 0.5 0.25 98 89 78 17
Comparative example 1 1 0 99 91 65 20
Embodiment 5 0.67 0.17 98 89 78 17
Embodiment 6 0.84 0.08 98 89 76 17
Embodiment 7 0.9 0.05 99 91 67 18
Embodiment 8 - 0.55 95 83 80 12
Table 2
There is not cyclic organic compounds with S=O key General expression Li m[Mn aNi bCo cO 2] in the value of c General expression Li m[Ni bM (1-b)O 2] in the value of b Initial stage discharge capacity (%) Initial stage efficient (%) High temperature charge-discharge performance (%) High temperature is preserved back self-discharge rate (%)
Comparative example 2 0.16 0.42 96 85 63 25
Comparative example 3 0.34 0.33 97 88 63 25
Comparative example 4 0.5 0.25 98 88 61 24
Comparative example 5 1 0 99 90 58 38
Comparative example 6 0.67 0.17 89 88 61 25
Comparative example 7 0.84 0.08 98 89 60 24
For above-mentioned battery of the present invention and battery relatively, the initial stage discharge capacity is roughly 100% of design capacity, and efficiency for charge-discharge also is roughly more than or equal to 80%.
At this, at the performance of test of high temperature charge and discharge cycles and high temperature preservation back self-discharge rate, with composition formula Li m[Mn aNi bCo cO 2] in make | the oxide sintered body of a-b|=0, c=0.16 is compared with comparison battery 2 as the battery of the present invention 2 of positive active material, and the battery of the present invention 2 of the use nonaqueous electrolyte that the present invention relates to does not more use the comparison battery 2 of the nonaqueous electrolyte that the present invention relates to improve significantly.
At with composition formula Li m[Mn aNi bCo cO 2] in make the LiCoO of c=1 2Be used for the comparison battery 1 of positive active material and compare battery 5, when carrying out same comparison, relatively relatively battery 5 is good for battery 1.But its effect may not just can be said so significantly.Hence one can see that, by being suitable for Li m[Mn aNi bCo cO 2] the oxide sintered body that to have value stratiform rock salt type crystal structure, that make above-mentioned c be 0≤c＜1 of (0≤m≤1.1, a+b+c=1, | a-b|≤0.05, a ≠ 0, b ≠ 0) expression, as the nonaqueous electrolyte of feature of the present invention, can give play to excellent especially effect.
Fig. 2 makes Li at battery 1～7 of the present invention and comparison battery 1～7 m[Mn aNi bCo cO 2] the value of c in (0≤m≤1.1, a+b+c=1, | a-b|≤0.05, a ≠ 0, b ≠ 0) is transverse axis, make the high temperature charge-discharge performance is the figure that the longitudinal axis is drawn.■ represents battery 1～7 of the present invention, compares battery 1, and ▲ expression is battery 2～7 relatively.
Fig. 3 makes Li at battery 1～8 of the present invention and comparison battery 1～7 m[Ni bM (1-b)O 2] the value of b in (M is Mn or Mn and Co, 0≤m≤1.1) is transverse axis, make the high temperature charge-discharge performance is the figure that the longitudinal axis is drawn.■ represents battery 1～8 of the present invention, compares battery 1, and ▲ expression is battery 2～7 relatively.
From these results, can know, consider from the angle of high temperature charge-discharge performance and high temperature preservation back self-discharge rate, use Li m[Mn aNi bCo cO 2] the value of c in the oxide sintered body with stratiform rock salt type crystal structure of (0≤m≤1.1, a+b+c=1, | a-b|≤0.05, a ≠ 0, b ≠ 0) expression is so long as 0≤c＜1 is just passable; When 0＜c≤0.84, can confirm that effect of the present invention is remarkable, be preferred therefore; When 0＜c≤0.5, can confirm that effect of the present invention is more remarkable, therefore more preferred; When 0＜c＜0.34, can confirm particular significant effect of the present invention, therefore preferred.
In addition,, can know, consider, use Li from the angle of high temperature charge-discharge performance and high temperature preservation back self-discharge rate from these results m[Ni bM (1-b)O 2] value of b in the oxide sintered body with stratiform rock salt type crystal structure of (M is Mn or Mn and Co, 0≤m≤1.1) expression is preferably the scope of 0.08≤b≤0.55; When 0.25≤b≤0.55, can confirm that effect of the present invention is more remarkable, therefore more preferred; When 0.33＜b＜0.55, can confirm particular significant effect of the present invention, therefore preferred.
In the above embodiments at using sulfolane, 1,3-propane sultone, 1, the 4-butane sultone is described as the example with cyclic organic compounds of S=O key, but uses the situation of glycol sulfite, the inferior propyl ester of sulfurous acid, cyclobufene sultone also to be identified same effect.
In addition, be described at the example that uses vinylene carbonate, the conduct of catechol carbonic ester to have the cyclic carbonate of carbon-to-carbon π key in the above embodiments, but use carbonic acid benzene ethyl, vinylethylene carbonate, carbonic acid-1-phenyl vinylene, carbonic acid-1, the situation of 2-diphenyl vinylene also is identified same effect.
And, be described at the example that uses ethylene carbonate, propylene carbonate conduct not to have the cyclic carbonate of carbon-to-carbon π key in the above embodiments, but use the situation of butylene carbonate also to be identified same effect.
In addition, for the present invention, only otherwise exceed its spirit or principal character, can implement with other various forms.Therefore, above-mentioned execution mode or embodiment be illustration only in all respects, not limited interpretation.Scope of the present invention is to be represented by the scope of claim, is not subjected to the constraint of specification text.And then, belong to the claim scope equal scope distortion or the change all within the scope of the invention.
The possibility of utilizing on the industry
As previously discussed, therefore the nonaqueous electrolyte battery that the present invention relates to can be effective as the e-machine that uses and preserve with power supply, electric vehicle power supply etc. with power supply, electric power because the battery performance under hot environment is excellent under hot environment.

Claims (12)

1. nonaqueous electrolyte battery, it is characterized in that, have positive pole and negative pole, by using the nonaqueous electrolyte contain the cyclic carbonate with carbon-to-carbon π key more than a kind or a kind respectively and to have the cyclic organic compounds of S=O key to make, and the principal component of positive active material that constitutes described positive pole is for using Li m[Ni bM (1-b)O 2] expression the oxide sintered body with stratiform rock salt type crystal structure, wherein, M is the element of 1～16 family more than a kind or a kind except Ni, Li and O, 0≤m≤1.1, the value of described b is 0.08≤b≤0.42.
2. nonaqueous electrolyte battery according to claim 1 is characterized in that, the value of described b is 0.25≤b≤0.42.
3. nonaqueous electrolyte battery according to claim 1 is characterized in that, described M is Mn or Mn and Co.
4. nonaqueous electrolyte battery according to claim 3 is characterized in that, described oxide sintered body is for using Li m[Mn aNi bCo cO 2] expression the oxide sintered body with stratiform rock salt type crystal structure, wherein, 0≤m≤1.1, a+b+c=1, | a-b|≤0.05, a ≠ 0, b ≠ 0, the value of described c is 0≤c＜1.
5. nonaqueous electrolyte battery according to claim 4 is characterized in that, the value of described c is 0＜c≤0.84.
6. nonaqueous electrolyte battery according to claim 5 is characterized in that, the value of described c is 0＜c≤0.5.
7. according to any described nonaqueous electrolyte battery of claim 1～6, it is characterized in that the cyclic organic compounds of the described S=O of having key has any one structure represented with Chemical formula 1～chemical formula 4.
Figure C2004800127850003C1
(Chemical formula 1)
Figure C2004800127850003C2
(Chemical formula 2)
Figure C2004800127850003C3
(chemical formula 3)
Figure C2004800127850003C4
(chemical formula 4)
8. nonaqueous electrolyte battery according to claim 7, it is characterized in that, the cyclic organic compounds of the described S=O of having key is for being selected from glycol sulfite, the inferior propyl ester of sulfurous acid, sulfolane, cyclobufene sultone, 1,3-propane sultone, 1, at least a in 4-butane sultone and their derivative.
9. according to any described nonaqueous electrolyte battery of claim 1～6, it is characterized in that, described cyclic carbonate with carbon-to-carbon π key is for being selected from vinylene carbonate, carbonic acid benzene ethyl, catechol carbonic ester, vinylethylene carbonate, carbonic acid-1-phenyl vinylene, carbonic acid-1, at least a in the 2-diphenyl vinylene.
10. according to any described nonaqueous electrolyte battery of claim 1～6, it is characterized in that described nonaqueous electrolyte contains the cyclic carbonate with carbon-to-carbon π key.
11. nonaqueous electrolyte battery according to claim 10 is characterized in that, the described cyclic carbonate that does not have carbon-to-carbon π key is to be selected from least a in ethylene carbonate, propylene carbonate, the butylene carbonate.
12. any described nonaqueous electrolyte battery according to claim 1～6 is characterized in that the principal component that constitutes the negative electrode active material of described negative pole is a graphite.
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