CN1848512A - Battery - Google Patents
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- CN1848512A CN1848512A CNA2006100740181A CN200610074018A CN1848512A CN 1848512 A CN1848512 A CN 1848512A CN A2006100740181 A CNA2006100740181 A CN A2006100740181A CN 200610074018 A CN200610074018 A CN 200610074018A CN 1848512 A CN1848512 A CN 1848512A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
A battery capable of improving the energy density and improving the cycle characteristics is provided. The battery includes a spirally wound electrode body, in which a cathode and an anode are wound with a separator and an electrolyte in between. The open circuit voltage in full charge is in the range from 4.25 V to 6.00 V. The electrolyte contains an electrolytic solution and a polymer containing vinylidene fluoride as a component. The polymer containing vinylidene fluoride as a component has high oxidation stability. Therefore, even when the battery voltage is raised, oxidation and decomposition of the electrolyte and the separator can be inhibited.
Description
The cross reference of related application
The present invention comprises the theme of the Japanese patent application JP2005-222038 that relates to the Japanese patent application JP 2005-107784 that submits to Japan Patent office on April 4th, 2005 and submit to Japan Patent office on July 29th, 2005, and its full content is hereby incorporated by.
Technical field
The present invention relates to battery, wherein the every pair of positive pole and the negative pole open circuit voltage under charged state fully is 4.25V or higher.
Background technology
In recent years, introduced many portable electric appts as combination camera, mobile phone and portable computer, and its size and weight reduce.In these electronic equipments, except size reduces, also promoted multi-functional and complicated.As a result, its power consumption is not always to reduce.In fact, since multi-functional, tend to service time become longer.The user expects to use this service time of longer portable electric appts.Therefore, expectation is widely used as the higher energy density of the lithium rechargeable battery of portable electric appts power supply.
Usually, in traditional lithium rechargeable battery, cobalt acid lithium is used for positive pole, and material with carbon element is used for negative pole, and operating voltage is in the scope of 4.2V-2.5V.In this lithium rechargeable battery of working under 4.2V to greatest extent, for being used for anodal positive electrode active materials such as cobalt acid lithium, only about 60% theoretical capacity is utilized.Therefore, in principle, can be by further increase charging voltage to utilize remaining capacity.In fact, known high-energy-density is 4.25V or higher realization the (referring to the open No.WO03/0197131 in the world) by setting charging voltage.
Summary of the invention
But, surpassing in the battery of 4.2V setting charging voltage, the oxidizing atmosphere oxidizing atmosphere of anodal near surface (particularly) strengthens.As a result, nonaqueous electrolyte material that contacts with anodal physics and barrier film are easy to oxidation and decomposition.Thereby such shortcoming is arranged: internal resistance increases, and battery behavior such as cycle characteristics reduce.
Consider above-mentioned shortcoming, in the present invention, even expectation provides the battery that also can improve battery behavior such as cycle characteristics when charging voltage surpasses 4.2V when setting.
According to the embodiment of the present invention, a kind of battery is provided, wherein anodal and negative pole has positioned opposite under the electrolytical situation therebetween, wherein the every pair of positive pole and the negative pole open circuit voltage under charged state fully is 4.25V-6.00V, and electrolyte comprises electrolyte and contains the polymer of vinylidene fluoride as component.
According to the battery of embodiment of the present invention, the open circuit voltage under complete charged state is 4.25V-6.00V owing to every pair of positive pole and negative pole, can obtain high-energy-density.In addition, because electrolyte comprises and contains the polymer of vinylidene fluoride as component, can be suppressed at the oxidation and the decomposition reaction of anodal near surface, and can improve battery behavior such as cycle characteristics.
Of the present invention other will embody from following description more fully with further purpose, feature and advantage.
Description of drawings
Fig. 1 is the decomposition diagram of displaying according to the structure of the secondary cell of embodiment of the present invention;
Fig. 2 is the cross section along the line I-I of spiral winding electrode shown in Figure 1;
Fig. 3 is for showing the performance plot of the relation between the cycle-index and discharge capacitance when charging voltage is 4.25V;
Fig. 4 is for showing the performance plot of the relation between the cycle-index and discharge capacitance when charging voltage is 4.55V;
Fig. 5 is for showing the performance plot of the relation between the cycle-index and discharge capacitance when charging voltage is 4.20V;
Fig. 6 is for showing according to charging voltage the performance plot that concerns between cycle-index and the discharge capacitance;
Fig. 7 is for showing according to charging voltage another performance plot that concerns between cycle-index and the discharge capacitance;
Fig. 8 is for showing according to charging voltage a performance plot again that concerns between cycle-index and the discharge capacitance; With
Fig. 9 is for showing according to charging voltage a performance plot again that concerns between cycle-index and the discharge capacitance.
Embodiment
Describe embodiments of the present invention below with reference to accompanying drawings in detail.
Fig. 1 has showed the structure according to the secondary cell of embodiment of the present invention.In this secondary cell, lithium (Li) is as the electrode reaction thing.For example, this secondary cell has such structure: the spiral winding electrode 10 that wherein is attached with positive wire 11 and negative wire 12 on it is included in film packaging element 20 inside.
For example positive wire 11 is guided the outside with identical direction into from packaging element 20 inside respectively with negative wire 12.Positive wire 11 and negative wire 12 are made by for example metal material such as aluminium (A1), copper (Cu), nickel (Ni) and stainless steel respectively, and are lamellar or netted.
Fig. 2 has showed along the cross-sectional structure of the line I-I of spiral winding electrode shown in Figure 1.In spiral winding electrode 10, a pair of anodal 13 and negative pole 14 and therebetween barrier film 15 and electrolyte 16 stacked and reel.Anodal 13 and negative pole 14 positioned opposite under the situation of barrier film 15 and electrolyte 16 is arranged therebetween.The outermost of spiral winding electrode 10 is by boundary belt 17 protections.
Anodal 13 have such structure: wherein for example anode active material layer 13B is provided on the two sides of the positive electrode collector 13A with a pair of opposite face.Although not shown, anode active material layer 13B can be provided on the only one side of positive electrode collector 13A.Positive electrode collector 13A is made by metal forming such as aluminium foil, nickel foil and stainless steel foil.Anode active material layer 13B comprises, and for example, one or more positive electrodes that can embed and deviate from lithium (it is the electrode reaction thing) are as positive electrode active materials.If necessary, anode active material layer 13B comprises electric conductor such as graphite and adhesive such as polyvinylidene fluoride.
As the positive electrode that can embed and deviate from lithium, for example, lithium-containing compound such as lithia, Lithium Phosphor Oxide (lithium phosphorous oxide), lithium sulfide and the intercalation compound that contains lithium are suitable.Can use its two or more by mixing.In order to improve energy density, preferably contain the lithium-containing compound of lithium, transition metal and oxygen (O).Especially, more preferably comprise at least a lithium-containing compound that is selected from cobalt (Co), nickel, manganese (Mn) and iron (Fe) as transition metal.As this lithium-containing compound, for example, can enumerate bedded salt (beddedsalt) the type lithium composite xoide shown in Chemical formula 1, Chemical formula 2 or the chemical formula 3; Spinel-type lithium composite xoide shown in the chemical formula 4; Olivine-type lithium composite phosphate shown in the chemical formula 5 etc.Especially, can enumerate LiNi
0.50CO
0.20Mn
0.30O
2, Li
aCoO
2(a ≈ 1), Li
bNiO
2(b ≈ 1), Li
C1Ni
C2Co
1-c2O
2(c1 ≈ 1,0＜c2＜1), LidMn
2O
4(d ≈ 1), Li
eFePO
4(e ≈ 1) etc.
(Chemical formula 1)
Li
fMn
(1-g-h)Ni
gM1
hO
(2-j)F
k
In formula, M1 represents to be selected from least a of cobalt, magnesium (Mg), aluminium, boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron, copper, zinc (Zn), zirconium (Zr), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr) and tungsten (W).F, g, h, j and k be in 0.8≤f≤1.2,0＜g＜0.5,0≤h≤0.5, g+h＜1 ,-value in 0.1≤j≤0.2 and 0≤k≤0.1 scope.The composition of lithium changes according to charging and discharge condition.Value under the complete discharge condition of the value representation of f.
(Chemical formula 2)
Li
mNi
(1-n)M2
nO
(2-p)F
q
In formula, M2 represents to be selected from least a of cobalt, manganese, magnesium, aluminium, boron, titanium, vanadium, chromium, iron, copper, zinc, molybdenum, tin, calcium, strontium and tungsten.M, n, p and q be in 0.8≤m≤1.2,0.005≤n≤0.5 ,-value in 0.1≤p≤0.2 and 0≤q≤0.1 scope.The composition of lithium changes according to charging and discharge condition.Value under the complete discharge condition of the value representation of m.
(chemical formula 3)
Li
rCo
(1-s)M3
sO
(2-t)F
u
In formula, M3 represents to be selected from least a of nickel, manganese, magnesium, aluminium, boron, titanium, vanadium, chromium, iron, copper, zinc, molybdenum, tin, calcium, strontium and tungsten.R, s, t and u be in 0.8≤r≤1.2,0≤s＜0.5 ,-value in 0.1≤t≤0.2 and 0≤u≤0.1 scope.The composition of lithium changes according to charging and discharge condition.Value under the complete discharge condition of the value representation of r.
(chemical formula 4)
Li
vMn
2-wM4
wO
xF
y
In formula, M4 represents to be selected from least a of cobalt, nickel, magnesium, aluminium, boron, titanium, vanadium, chromium, iron, copper, zinc, molybdenum, tin, calcium, strontium and tungsten.V, w, x and y are the value in 0.9≤v≤1.1,0≤w≤0.6,3.7≤x≤4.1 and 0≤y≤0.1 scope.The composition of lithium changes according to charging and discharge condition.Value under the complete discharge condition of the value representation of v.
(chemical formula 5)
Li
zM5PO
4
In formula, M5 represents to be selected from least a of cobalt, manganese, iron, nickel, magnesium, aluminium, boron, titanium, vanadium, niobium, copper, zinc, molybdenum, calcium, strontium, tungsten and zirconium.Z is the value in 0.9≤z≤1.1 scopes.The composition of lithium changes according to charging and discharge condition.Value under the complete discharge condition of the value representation of z.
As the positive electrode that can embed and deviate from lithium, except above-mentioned, also can enumerate the inorganic compound such as the MnO that do not contain lithium
2, V
2O
5, V
6O
13, NiS and MoS.
Negative pole 14 has such structure: wherein anode active material layer 14B is provided on the two sides of the negative electrode collector 14A with a pair of opposite face.Although not shown, anode active material layer 14B can only be provided on the one side of negative electrode collector 14A.Negative electrode collector 14A is made by for example metal forming such as Copper Foil, nickel foil and stainless steel foil, and it has favourable electrochemical stability, conductivity and mechanical strength.Especially, Copper Foil most preferably is because Copper Foil has high conductivity.
Anode active material layer 14B comprises one or more can embed and deviate from the negative material of lithium as negative active core-shell material.If necessary, anode active material layer 14B comprises and the similar adhesive of the adhesive of anode active material layer 13B.
As the negative material that can embed and deviate from lithium, for example, but but can enumerate material with carbon element such as non--graphitized carbon graphitized carbon, graphite, RESEARCH OF PYROCARBON, coke, vitreous carbon, organic polymer quantification compound sintered body, carbon fiber and active carbon.In above-mentioned, coke comprises pitch coke, needle coke, petroleum coke etc.Organic polymer quantizes the compound sintered body by under suitable temperature high-molecular weight compounds such as phenolic resins and furane resins roasting and carbonization being obtained, but but and some of them can be categorized as non--graphitized carbon or graphitized carbon.As high molecular weight material, can enumerate polyacetylene, polypyrrole etc.These material with carbon elements are preferred, because the changes in crystal structure that produces in charging and discharge is very little, can obtains high charging and discharge capacity, and can obtain favourable cycle characteristics.Especially, preferred graphite because electrochemical equivalent is big, and can obtain high-energy-density.In addition, but preferred non--graphitized carbon, because can obtain excellent characteristic.And, preferably have the material of low charging and discharge potential, particularly have the charging that approaches the lithium metal and the material of discharge potential, because can easily realize the high-energy-density of battery thus.
As the negative material that can embed and deviate from lithium, also can enumerate to embed and to deviate from lithium and comprise metallic element and at least a material of metalloid element as element.When using this material, can obtain high-energy-density.Especially, this material more preferably uses with material with carbon element, because can obtain high-energy-density, and can obtain excellent cycle characteristics.This negative material can be simple substance, alloy or the compound of metallic element or metalloid element, or can have its one or more phases to small part.In the present invention, except the alloy that comprises two or more metallic elements, alloy also comprises the alloy that contains one or more metallic elements and one or more metalloid elements.In addition, alloy can comprise nonmetalloid.Its structure (texture) comprises solid solution, eutectic crystal (eutectic mixture), intermetallic compound and the structure of its two or more coexistences wherein.
As the metallic element or the metalloid element that constitute negative material, can enumerate magnesium, boron, aluminium, gallium (Ga), indium (In), silicon (Si), germanium (Ge), tin, lead (Pb), bismuth (Bi), cadmium (Cd), silver (Ag), zinc, hafnium (Hf), zirconium, yttrium (Y), palladium (Pd) or platinum (Pt).They can be crystallization or unbodied.
Especially, as negative material, preferably comprise the metallic element of 4B family in the short period periodic table of elements or metalloid element material as element.At least a material of preferred especially siliceous and tin as element.The ability that silicon and tin have high embedding and deviates from lithium, and high-energy-density can be provided.
As the alloy of tin, for example, can enumerate and comprise at least a alloy that is selected from silicon, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony (Sb) and chromium as the second outer element of detin.As the alloy of silicon, for example, can enumerate and comprise at least a alloy that is selected from tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony and chromium as the second outer element of silica removal.
As the compound of tin or the compound of silicon, for example, can enumerate the compound that comprises oxygen or carbon (C).Except tin or silicon, compound also can comprise above-mentioned second element.
As the negative material that can embed and deviate from lithium, can further enumerate other metallic compounds or high molecular weight material.As other metallic compounds, can enumerate oxide such as MnO
2, V
2O
5And V
6O
13Sulfide such as NiS and MoS; Or lithium nitride such as LiN
3As high molecular weight material, can enumerate polyacetylene, polyaniline, polypyrrole etc.
In addition, in this secondary cell,, will be set in the scope of 4.25V-6.00V at the open circuit voltage (being cell voltage) under charging fully by regulating the amount of positive electrode active materials and negative active core-shell material.Thereby, can obtain high-energy-density.For example, the open circuit voltage under charging fully is under 4.25V or the higher situation, even use identical positive electrode active materials, the lithium of per unit weight is deviate from the battery that quantitative change must be 4.2V than the open circuit voltage under charging fully big.Therefore, regulate the amount of negative active core-shell material.
The perforated membrane that barrier film 15 is made by synthetic resin such as polytetrafluoroethylene, polypropylene and polyethylene, or ceramic porous membrane is made.Barrier film 15 can have wherein two or more porous membrane laminated structures of perforated membrane as mentioned above.Especially, the preferred polyolefm perforated membrane is because this film has excellent anti-short circuit effect and can improve battery security by blackout effect (shutdown effect).
Electrolyte 16 comprises electrolyte and keeps the high-molecular weight compounds of this electrolyte, and is so-called gel.Electrolyte comprises solvent and electrolytic salt.
As solvent, for example, can enumerate nonaqueous solvents such as lactone such as gamma-butyrolacton, gamma-valerolactone, δ-Wu Neizhi and 6-caprolactone; Carbonic ester such as ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate; Ether is as 1,2-dimethoxy-ethane, 1-ethyoxyl-2-Ethyl Methyl Ether, 1,2-diethoxyethane, oxolane and 2-methyltetrahydrofuran; Ester such as methyl propionate; Sulfoxide such as dimethyl sulfoxide (DMSO); Nitrile such as acetonitrile; Sulfolane; Phosphoric acid; Phosphate; Pyrrolidones; And derivative.Can use a kind of of these solvents separately, maybe can use its two or more by mixing.
For electrolytic salt, for example, can enumerate lithium salts.Can be used alone lithium salts, maybe can use its two or more by mixing.As lithium salts, can enumerate LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiClO
3, LiBrO
3, LiIO
3, LiNO
3, LiCH
3COO, LiB (C
6H
5)
4, LiCH
3SO
3, LiCF
3SO
3, LiN (SO
2CF
3)
2, LiC (SO
2CF
3)
3, LiAlCl
4, LiSiF
6, LiCl, LiBr, LiI, difluoro [oxolation (oxolate)-O-O '] lithium borate, lithium dioxalic acid salt borate (lithium bis oxalate borate) etc.Especially, preferred LiPF
6And LiBF
4, because LiPF
6And LiBF
4Has high oxidation stability.
High-molecular weight compounds comprises and contains the polymer of vinylidene fluoride as component.Thus, can improve the oxidation stability of electrolyte 16, even and when cell voltage raises, can be suppressed at oxidation and decomposition reactions near anodal 13.This polymer can be polyvinylidene fluoride or contains the copolymer of vinylidene fluoride as component.Can be used alone polymer, maybe can use two or more polymer by mixing.In addition, other one or more high-molecular weight compounds can with contain the polymer mixed of vinylidene fluoride as component.
As the cyclic carbonate such as the vinylene carbonate that contain the copolymer of vinylidene fluoride, can enumerate the monoesters that comprises for example hexafluoropropylene, unsaturated dibasic acid such as monomethyl maleate, ethylene halide such as chlorotrifluoroethylene (ethylenechloride trifluoride), unsaturated compound or contain the copolymer of the acryloyl group vinyl monomer of epoxide group as other components as component.Other components can be one or more.
Especially, as polymer, preferably contain vinylidene fluoride and hexafluoropropylene copolymer as component.This copolymer has high contact performance and dipping characteristic to electrode, and excellent battery behavior is provided.Especially, preferred its block copolymer is because this block copolymer can provide high characteristic.In copolymer, the copolymerization amount of hexafluoropropylene is preferably 7 weight % or littler.When the copolymerization amount of hexafluoropropylene was too big, the base material crystallinity of polymer changed, and mechanical strength and keep the ability of electrolyte to reduce.
Electrolyte 16 preferably be clipped at least anodal 13 and barrier film 15 between.As mentioned above, contain the polymer of vinylidene fluoride as component because electrolyte 16 comprises, electrolyte 16 has high oxidation stability.Therefore, electrolyte 16 can suppress barrier film 15 and contacts and oxidation and decomposition with anodal 13.In this embodiment, as shown in Figure 2, electrolyte 16 is provided at respectively between positive pole 13 and the barrier film 15, and between negative pole 14 and the barrier film 15.
For example, this secondary cell of following manufacturing.
At first, for example, form anodal 13 by on positive electrode collector 13A, forming anode active material layer 13B.For example, following formation anode active material layer 13B.Positive electrode, electric conductor and the adhesive that can embed and deviate from lithium mix with the preparation cathode mix, and it is dispersed in solvent such as the N-N-methyl-2-2-pyrrolidone N-to obtain pasty state cathode mix slurry.Then, apply positive electrode collector 13A with this cathode mix slurry, dry solvent, and by roll squeezer compression molding product.Thereby, form anode active material layer 13B.
In addition, for example, by on negative electrode collector 14A, forming anode active material layer 14B to form negative pole 14.Anode active material layer 14B can be by two or more any one formation of combination of for example vapour deposition process, liquid phase deposition, sintering process, coating and these methods.As vapour deposition process, for example, can use physical deposition method or chemical deposition.Especially, can utilize vaccum gas phase sedimentation method, sputtering method, ion plating, laser ablation method, hot CVD (chemical vapour deposition (CVD)) method, plasma CVD method etc.As liquid phase deposition, can utilize known technology as electroplating and chemical plating.For sintering process, can utilize known technology such as atmosphere sintering method (atmosphere firing method), reactive sintering process (reactive firing method) and hot pressing sintering method.Under situation about applying, anode active material layer 14B can the mode identical with anodal 13 form.
Then, apply positive pole 13 and negative pole 14 by using the precursor solution that comprises electrolyte, high-molecular weight compounds and mixed solvent, and make the mixed solvent volatilization then, form electrolyte 16.Afterwards, positive wire 11 is attached to positive electrode collector 13A, and negative wire 12 is attached to negative electrode collector 14A.Subsequently, will be formed with the positive pole 13 of electrolyte 16 and negative pole 14 is stacked with barrier film 15 therebetween.In the vertical this sandwich is reeled, and boundary belt 17 is adhered to outermost to form spiral winding electrode 10.At last, for example, spiral winding electrode 10 is clipped between the packaging element 20, and the outer rim of packaging element 20 is by contacts such as thermofussion weldings, and sealing screw rolled electrode body 10.Then, adhesive film 21 is inserted between positive wire 11, negative wire 12 and the packaging element 20.Obtain the secondary cell shown in Fig. 1 and 2 thus.
In this secondary cell, when charging, lithium ion is deviate from from anode active material layer 13B and is embedded among the anode active material layer 14B by electrolyte 16.Then, when discharge, lithium ion is deviate from from anode active material layer 14B, and embeds among the anode active material layer 13B by electrolyte 16.In this embodiment, the open circuit voltage height under charging fully is 4.25V or higher, and is in the strong oxidizing atmosphere near anodal 13.But,, suppressed oxidation and decomposition reaction near anodal 13 because electrolyte 16 comprises and contains the polymer of vinylidene fluoride as component.
As above, in this embodiment, because the every pair of positive pole 21 and negative pole 22 are in the scope of open circuit voltage at 4.25V-6.00V under the charging fully.Therefore, can obtain high-energy-density.In addition, because electrolyte 16 comprises and contains the polymer of vinylidene fluoride as component,, also be suppressed near anodal 13 oxidation and decomposition reactions even when the open circuit voltage under charging fully raises.Thereby, can improve battery behavior such as cycle characteristics.
Embodiment
In addition, will describe specific embodiments of the invention in detail.
(embodiment 1-1 and 1-2)
Make secondary cell as illustrated in fig. 1 and 2.At first, following formation positive electrode active materials.As the aqueous solution, nickel nitrate, cobalt nitrate and the manganese nitrate that is purchased mixed, so that the ratio of Ni, Co and Mn is respectively 0.333,0.334 and 0.333.Afterwards, when fully stirring the mixture, ammoniacal liquor is added drop-wise in this mixed solution, to obtain complex hydroxide.This complex hydroxide and lithium hydroxide are mixed, with this mixture under 900 ℃ in Oxygen Flow sintering 10 hours, and pulverize to obtain the lithium composite xoide powder as positive electrode active materials.When analyzing the lithium composite xoide powder of acquisition, confirm to consist of LiNi by atomic absorption spectrum (ASS)
0.33Co
0.33Mn
0.33O
2In addition, when measuring particle diameter by laser diffractometry, average grain diameter is 13 μ m.In addition, when carrying out the X-ray diffraction measurement, confirm that measurement result is similar to listed LiNiO in ICDD (diffraction data International Centre) card No.09-0063
2Pattern, and formed and LiNiO
2Similar bedded salt structure.And, when observing the lithium composite xoide powder that obtains, observe the spheric granules of the primary granule reunion that wherein is of a size of 0.1 μ m-5 μ m by scanning electron microscopy (SEM).
Then, the LiNi that 86 weight % are obtained
0.33Co
0.33Mn
0.33O
2Powder, 10 weight % mix as the polyvinylidene fluoride of adhesive as the Delanium powder of electric conductor and 4 weight %.This mixture is dispersed in as starching to obtain cathode mix in the N-N-methyl-2-2-pyrrolidone N-of solvent.Subsequently, starch the two sides that applies the positive electrode collector 13A that is made by the bar shaped aluminium foil of thick 20 μ m equably with this cathode mix, it is dried and also forms positive pole 13 by the roll squeezer compression molding thus to form anode active material layer 13B.
In addition, preparation spherical graphite powder is as negative active core-shell material.Spherical graphite powder and the 10 weight % of 90 weight % are mixed as the vinylidene fluoride of adhesive and the copolymer of hexafluoropropylene.This mixture is dispersed in as starching to obtain the negative pole mixture in the N-N-methyl-2-2-pyrrolidone N-of solvent.Then, starch the two sides that applies the negative electrode collector 14A that makes by the bar shaped Copper Foil of thick 10 μ m equably, it is carried out hot press molding to form anode active material layer 14B and to form negative pole 14 thus with this negative pole mixture.For positive pole 13 and negative pole 14, regulate the coated weight of positive electrode active materials and negative active core-shell material, so that under predetermined charge voltages, the theoretical lithium of anodal 13 per unit area is deviate from amount and is become positive pole/negative pole=0.95 with respect to the ratio of the theoretical lithium embedded quantity of the per unit area of anodal 13 negative pole 14.So charging voltage is 4.25V in embodiment 1-1, and in embodiment 1-2 4.55V.
Subsequently, with 42.5 weight % ethylene carbonates, 42.5 weight % propylene carbonates and 15 weight %LiPF
6Mixing is with preparation electrolyte.With this electrolyte of 30 weight portions and 10 weight portion weight average molecular weight is that the block copolymer of about 600000 vinylidene fluoride and hexafluoropropylene mixes and by using the mixed solvent dissolving to form precursor solution.Afterwards, with the two sides of this precursor solution coating anodal 13 and negative pole 14, make this mixed solution volatilization, and form electrolyte 16 respectively.Then, positive wire 11 is attached on the positive electrode collector 13A, and negative wire 12 is attached on the negative electrode collector 14A.
Subsequently, it is stacked and reel with the barrier film of being made by many microporous polyolefin films therebetween to be formed with the positive pole 13 of electrolyte 16 and negative pole 14, to form spiral winding electrode 10.Afterwards.Spiral winding electrode 10 is clipped between the packaging element of being made by the aluminium lamination press mold 20.The edge (peripheral edge) that encloses of packaging element 20 is contacted with each other, and sealing screw rolled electrode body 10.Thereby, the secondary cell of acquisition embodiment 1-1 and 1-2.
As comparative example 1-1 and 1-2 with respect to embodiment 1-1 and 1-2, make secondary cell in the mode identical with 1-2 with embodiment 1-1, except electrolyte is directly injected packaging element, do not contain beyond the polymer of vinylidene fluoride as component and do not use.In addition, 1-3 and 1-4 as a comparative example, make secondary cell in the mode identical with 1-2 with embodiment 1-1, except when charging voltage is 4.20V, regulate beyond the coated weight of positive electrode active materials and negative active core-shell material, and except in comparative example 1-4, do not use polymer in addition, electrolyte is directly injected beyond the packaging element.
For the secondary cell that embodiment 1-1 and 1-2 and comparative example 1-1 to 1-4 make, charge and discharge, and detect the discharge capacitance of discharge capacity that at every turn circulates to the circulation time first time.Then,, under 23 ℃, in 2 hours, make under the current value that theoretical capacity discharges fully, carry out constant current charge after cell voltage reaches particular value, under specific constant voltage, carry out constant voltage charge 5 hours to obtain complete charged state for charging.This specific voltage value is 4.25V in embodiment 1-1 and comparative example 1-1, is 4.55V in embodiment 1-2 and comparative example 1-2, and is 4.20V in comparative example 1-3 and 1-4.For discharge, under 23 ℃, in 2 hours, make under the current value that theoretical capacity discharges fully, carry out constant-current discharge and reach 3.0V, and obtain complete discharge condition up to cell voltage.What obtain the results are shown among Fig. 3-5.
Shown in Fig. 3-5, charging voltage is among 4.25V or the higher embodiment 1-1 and 1-2 and comparative example 1-1 and 1-2 therein, use contains vinylidene fluoride to be compared with 1-2 with the comparative example 1-1 of direct use electrolyte with 1-2 as the embodiment 1-1 of the polymer of component, and the reduction of discharge capacity can be less.Especially, (charging voltage height wherein, 4.55V) relatively the time, the discharge capacitance of embodiment 1-2 can significantly improve than the discharge capacitance of comparative example 1-2 as embodiment 1-2 and comparative example 1-2.Simultaneously, charging voltage is among the comparative example 1-3 and 1-4 of 4.20V therein, no matter whether use polymer, discharge capacitance almost is equal to each other.
That is, find can to improve the oxidation stability of electrolyte 16 as long as use and contain the polymer of vinylidene fluoride as component, even and when the open circuit voltage under charging fully be 4.25V or when higher, also can obtain the cycle characteristics of excellence.
(embodiment 2-1,2-2,3-1 and 3-2)
Make secondary cell in the mode identical with 1-2,, in embodiment 2-1 and 2-2, use LiCoO except as positive electrode active materials with embodiment 1-1
2Powder and in embodiment 3-1 and 3-2, use LiCo
0.98Al
0.01Mg
0.01O
2Powder; And predetermined charging voltage be 4.40V in embodiment 2-1, is 4.55V in embodiment 2-2, is 4.40V in embodiment 3-1 and is beyond the 4.55V in embodiment 3-2.
As with respect to the comparative example 2-1 of embodiment 2-1 and 2-2 and 2-2, and as comparative example 3-1 and 3-2 with respect to embodiment 3-1 and 3-2, make secondary cell in the mode identical with 3-2 with embodiment 2-1 and 2-2 or embodiment 3-1, except electrolyte is directly injected packaging element, do not contain beyond the polymer of vinylidene fluoride as component and do not use.In addition, 2-3 and 2-4, and comparative example 3-3 and 3-4 as a comparative example, make battery in the mode identical with 3-2 with embodiment 2-1 and 2-2 or embodiment 3-1, except when charging voltage is 4.20V, regulate beyond the coated weight of positive electrode active materials and negative active core-shell material, and except in comparative example 2-4 and 3-4, do not use polymer in addition, electrolyte is directly injected beyond the packaging element.
Secondary cell for embodiment 2-1,2-2,3-1 and 3-2 and comparative example 2-1 to 2-4 and 3-1 to 3-4 manufacturing, charge and discharge in the mode identical with 1-2, and detect the discharge capacitance of discharge capacity of each circulation the circulation time first time with embodiment 1-1.Specific voltage value in charging is 4.40V in embodiment 2-1 and 3-1 and comparative example 2-1 and 3-1; In embodiment 2-2 and 3-2 and comparative example 2-2 and 3-2 is 4.55V; And in comparative example 2-3,2-4,3-3 and 3-4 4.20V.Obtain the results are shown in table 1 and 2 and Fig. 6-9 in.
Table 1
| Charging voltage (V) | Positive electrode active materials | Electrolyte | Discharge capacitance (%) | |||
| The 100th circulation | The 200th circulation | The 400th circulation | ||||
| Embodiment 2-1 | 4.40 | LiCoO 2 | Comprise polymer | 98.6 | 92.1 | 84.0 |
| Embodiment 2-2 | 4.55 | 90.6 | 84.0 | 76.0 | ||
| Comparative example 2-1 | 4.40 | LiCoO 2 | No polymer | 92.1 | 59.6 | 0 |
| Comparative example 2-2 | 4.55 | 88.3 | 40.1 | 0 | ||
| Comparative example 2-3 | 4.20 | Comprise polymer | 99.0 | 94.4 | 88.0 | |
| Comparative example 2-4 | No polymer | 98.9 | 94.0 | 87.7 | ||
Table 2
| Charging voltage (V) | Positive electrode active materials | Electrolyte | Discharge capacitance (%) | |||
| The 100th circulation | The 200th circulation | The 400th circulation | ||||
| Embodiment 3-1 | 4.40 | LiCo 0.98Al 0.01 Mg 0.01O 2 | Comprise polymer | 97.5 | 95.4 | 89.3 |
| Embodiment 3-2 | 4.55 | 95.7 | 92.1 | 87.2 | ||
| Comparative example 3-1 | 4.40 | LiCo 0.98Al 0.01 Mg 0.01O 2 | No polymer | 92.4 | 62.5 | 0 |
| Comparative example 3-2 | 4.55 | 90.3 | 41.4 | 0 | ||
| Comparative example 3-3 | 4.20 | Comprise polymer | 99.1 | 95.0 | 90.0 | |
| Comparative example 3-4 | No polymer | 99.0 | 94.2 | 88.6 | ||
Shown in table 1 and 2, the same at embodiment 1-1 and 1-2, surpass under the situation of 4.20V in charging voltage, use contains vinylidene fluoride to be compared with comparative example 2-1,2-2,3-1 and the 3-2 of direct use electrolyte as embodiment 2-1,2-2,3-1 and the 3-2 of the polymer of component, and discharge capacitance can significantly improve.Simultaneously, charging voltage is among comparative example 2-3,2-4,3-3 and the 3-4 of 4.20V therein, no matter whether use polymer, discharge capacitance almost is equal to each other.
That is, find as long as use contains the polymer of vinylidene fluoride as component, even when using other positive electrode active materials, also can obtain similar effects.
(embodiment 4-1 to 4-10,5-1 to 5-9,6-1 and 6-2)
Make secondary cell in the mode identical with 1-2,,, use LiCoO as positive electrode active materials except in embodiment 4-1 to 4-9 with embodiment 1-1
2Powder and LiNi
0.33Co
0.33Mn
0.33O
2The mixture of powder and predetermined charge voltages are beyond the 4.40V and except in embodiment 4-10, as positive electrode active materials, use LiNi
0.33Co
0.33Mn
0.33O
2Powder and predetermined charge voltages are beyond the 4.40V.
In embodiment 5-1 to 5-9, make secondary cell in the mode identical with 1-2 with embodiment 1-1, except as positive electrode active materials, use LiCoO
2Powder and LiNi
0.33Co
0.33Mn
0.33O
2The mixture of powder and predetermined charge voltages are beyond the 4.55V.
In embodiment 6-1 and 6-2, make secondary cell in the mode identical with 1-2 with embodiment 1-1, except as positive electrode active materials, use LiCo
0.98Al
0.01Mg
0.01O
2Powder and LiNi
0.33Co
0.33Mn
0.33O
2The mixture of powder and predetermined charge voltages are beyond 4.40V or the 4.55V.
The secondary cell of making for embodiment 4-1 to 4-10,5-1 to 5-9,6-1 and 6-2 charges and discharge in the mode identical with 1-2 with embodiment 1-1, and detects the discharge capacitance of discharge capacity that at every turn circulates to the circulation time first time.Scheduled voltage in charging is 4.40V in embodiment 4-1 to 4-10 and 6-1; And in embodiment 5-1 to 5-9 and 6-2 4.55V.The result who obtains is shown among the table 3-5 with the result of embodiment 1-2,2-1,2-2,3-1 and 3-2.
Table 3
Charging voltage: 4.40V
| Positive electrode active materials is formed (weight ratio) | Discharge capacitance (%) | ||||
| LiCoO 2 | LiNi 0.33Co 0.33Mn 0.33O 2 | The 100th circulation | The 200th circulation | The 400th circulation | |
| Embodiment 2-1 | 10 | 0 | 98.6 | 92.1 | 84.0 |
| Embodiment 4-1 | 9 | 1 | 98.8 | 91.8 | 84.0 |
| Embodiment 4-2 | 8 | 2 | 98.3 | 91.7 | 83.9 |
| Embodiment 4-3 | 7 | 3 | 98.0 | 91.7 | 84.3 |
| Embodiment 4-4 | 6 | 4 | 98.1 | 91.9 | 84.5 |
| Embodiment 4-5 | 5 | 5 | 97.9 | 92.0 | 84.6 |
| Embodiment 4-6 | 4 | 6 | 98.6 | 91.8 | 84.5 |
| Embodiment 4-7 | 3 | 7 | 98.0 | 92.1 | 84.7 |
| Embodiment 4-8 | 2 | 8 | 98.4 | 92.0 | 84.6 |
| Embodiment 4-9 | 1 | 9 | 98.3 | 92.4 | 84.8 |
| Embodiment 4-10 | 0 | 10 | 98.5 | 93.0 | 84.9 |
Table 4
Charging voltage: 4.55V
| Positive electrode active materials is formed (weight ratio) | Discharge capacitance (%) | ||||
| LiCoO 2 | LiNi 0.33Co 0.33Mn 0.33O 2 | The 100th circulation | The 200th circulation | The 400th circulation | |
| Embodiment 2-2 | 10 | 0 | 90.6 | 84.0 | 76.0 |
| Embodiment 5-1 | 9 | 1 | 90.6 | 84.3 | 76.2 |
| Embodiment 5-2 | 8 | 2 | 90.9 | 84.0 | 76.1 |
| Embodiment 5-3 | 7 | 3 | 91.1 | 84.8 | 76.8 |
| Embodiment 5-4 | 6 | 4 | 92.2 | 85.1 | 77.6 |
| Embodiment 5-5 | 5 | 5 | 92.1 | 85.2 | 77.3 |
| Embodiment 5-6 | 4 | 6 | 92.7 | 85.8 | 78.6 |
| Embodiment 5-7 | 3 | 7 | 93.1 | 87.0 | 79.9 |
| Embodiment 5-8 | 2 | 8 | 93.8 | 87.9 | 81.0 |
| Embodiment 5-9 | 1 | 9 | 94.3 | 90.0 | 81.5 |
| Embodiment 1-2 | 0 | 10 | 94.7 | 90.2 | 82.0 |
Table 5
| Charging voltage (V) | Positive electrode active materials is formed (weight ratio) | Discharge capacitance (%) | ||||
| LiCo 0.98Al 0.01 Mg 0.01O 2 | LiNi 0.33Co 0.33 Mn 0.33O 2 | The 100th circulation | The 200th circulation | The 400th circulation | ||
| Embodiment 3-1 | 4.40 | 10 | 0 | 97.5 | 95.4 | 89.3 |
| Embodiment 6-1 | 7 | 3 | 96.9 | 94.5 | 89.6 | |
| Embodiment 3-2 | 4.55 | 10 | 0 | 95.7 | 92.1 | 87.2 |
| Embodiment 6-2 | 7 | 3 | 96.1 | 93.5 | 86.0 | |
As show shown in the 3-5, even when using the mixture of positive electrode active materials, also can obtain the result who equates with embodiment 1-2, the 2-1,2-2,3-1 and the 3-2 that wherein are used alone positive electrode active materials.That is, find as long as use contains the polymer of vinylidene fluoride as component, even when using the mixture of positive electrode active materials, also can obtain similar effects.
With reference to execution mode and embodiment the present invention has been described.But, the invention is not restricted to above-mentioned execution mode and the foregoing description, and can carry out various changes.For example, in the above-described embodiment and examples, provided and used the description of lithium as the situation of electrode reaction thing.But the present invention can be applicable to use the situation of the alloy of other 1A family elements such as sodium (Na) and potassium (K), 2A family element such as magnesium and calcium (Ca), other light metals such as aluminium or lithium or above-mentioned element, and can obtain similar effects thus.Then, for negative active core-shell material, can use the negative material of describing in the above-described embodiment similarly.
In addition, in the above-described embodiment and examples, to its septation 15 and electrolyte 16 be provided at anodal 13 and negative pole 14 between situation provided description.But,, can save barrier film 15 when by for example insulating packing being mixed with electrolyte can guarantee to insulate fully the time.
In addition, in the above-described embodiment and examples, to having wherein anodal 13 and negative pole 14 is stacked and the secondary cell of the screw winding structure of reeling has provided description.But the present invention can be applied to have wherein anodal and the folding structure of negative pole similarly, or the secondary cell wherein anodal and structure that negative pole is stacked.Except the film packaging element, also can use the shell packaging element.In addition, the present invention can be applied to secondary cell such as so-called Coin shape secondary cell, button type secondary cell, cylinder type secondary battery and square secondary cell similarly.And except secondary cell, the present invention can be applicable to primary cell.
It will be appreciated by those skilled in the art that in the scope of claims or its equivalent, depend on designing requirement and other factors, can carry out various changes, combination, recombinant and replacement.
Claims (4)
1. battery, wherein anodal and negative pole has positioned opposite under the electrolytical situation therebetween,
Wherein the every pair of positive pole and the negative pole open circuit voltage under charged state fully is 4.25V-6.00V, and
This electrolyte comprises electrolyte and comprises the polymer of vinylidene fluoride as component.
2. the battery of claim 1, wherein this polymer comprises and contains vinylidene fluoride and the hexafluoropropylene copolymer as component.
3. the battery of claim 2, wherein in this copolymer, the copolymerization amount of hexafluoropropylene is 7 weight % or littler.
4. the battery of claim 1, wherein this positive pole comprises and is selected from least a of the lithium composite xoide shown in Chemical formula 1, Chemical formula 2 or the chemical formula 3
(Chemical formula 1)
Li
fMn
(1-g-h)Ni
gM1
hO
(2-j)F
k
Wherein M1 represents to be selected from least a of cobalt (Co), magnesium (Mg), aluminium (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), zirconium (Zr), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr) and tungsten (W); And f, g, h, j and k be in 0.8≤f≤1.2,0＜g＜0.5,0≤h≤0.5, g+h＜1 ,-value in 0.1≤j≤0.2 and 0≤k≤0.1 scope;
(Chemical formula 2)
Li
mNi
(1-n)M2
nO
(2-p)F
q
Wherein M2 represents to be selected from least a of cobalt, manganese, magnesium, aluminium, boron, titanium, vanadium, chromium, iron, copper, zinc, molybdenum, tin, calcium, strontium and tungsten; And m, n, p and q be in 0.8≤m≤1.2,0.005≤n≤0.5 ,-value in 0.1≤p≤0.2 and 0≤q≤0.1 scope;
(chemical formula 3)
Li
rCo
(1-s)M3
sO
(2-t)F
u
Wherein M3 represents to be selected from least a of nickel, manganese, magnesium, aluminium, boron, titanium, vanadium, chromium, iron, copper, zinc, molybdenum, tin, calcium, strontium and tungsten; And r, s, t and u be in 0.8≤r≤1.2,0≤s＜0.5 ,-value in 0.1≤t≤0.2 and 0≤u≤0.1 scope.
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|---|---|---|---|
| JP107784/05 | 2005-04-04 | ||
| JP2005107784 | 2005-04-04 | ||
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105811004A (en) * | 2014-12-30 | 2016-07-27 | 浙江蓝天环保高科技股份有限公司 | Gel electrolyte for lithium ion battery |
| CN108370066A (en) * | 2016-03-10 | 2018-08-03 | 株式会社吴羽 | Gel-like electrolyte with and preparation method thereof |
-
2006
- 2006-04-04 CN CNA2006100740181A patent/CN1848512A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105811004A (en) * | 2014-12-30 | 2016-07-27 | 浙江蓝天环保高科技股份有限公司 | Gel electrolyte for lithium ion battery |
| CN108370066A (en) * | 2016-03-10 | 2018-08-03 | 株式会社吴羽 | Gel-like electrolyte with and preparation method thereof |
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