CN101099251A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary battery Download PDFInfo
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- CN101099251A CN101099251A CNA2006800017862A CN200680001786A CN101099251A CN 101099251 A CN101099251 A CN 101099251A CN A2006800017862 A CNA2006800017862 A CN A2006800017862A CN 200680001786 A CN200680001786 A CN 200680001786A CN 101099251 A CN101099251 A CN 101099251A
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- mixture layer
- negative pole
- active material
- ditch
- nonaqueous electrolytic
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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
Abstract
Disclosed is a nonaqueous electrolyte secondary battery comprising a negative electrode, a positive electrode and a nonaqueous electrolyte arranged between the electrodes. A negative electrode mix layer containing at least an active material capable of adsorbing and desorbing lithium ions is formed on at least one surface of a collector of the negative electrode. The negative electrode mix layer is provided with a plurality of parallel mix layer expansion adsorbing grooves in a position where the negative electrode mix layer faces the positive electrode mix layer, so that the collector is exposed from the grooves.
Description
Technical field
The present invention relates to rechargeable nonaqueous electrolytic battery, say in further detail, relate to the good rechargeable nonaqueous electrolytic battery of charge-discharge characteristic that has used jumbo negative pole.
Background technology
Along with the portability of electronic equipment, the progress of wirelessization, increase day by day for small-sized, light weight and expectation with rechargeable nonaqueous electrolytic battery of high-energy-density.Under such situation, material with carbon elements such as present graphite are practical as the negative electrode active material of rechargeable nonaqueous electrolytic battery.Then, in order further to reach high energy density, based on the research well afoot of the packed density that improves the active material in the electrode.
On the other hand, the theoretical capacity density of material with carbon element such as graphite is 372mAh/g.Here, in order further to make the rechargeable nonaqueous electrolytic battery high-energy-densityization, studying with theoretical capacity density big with silicon lithium alloyage (Si), tin (Sn), germanium (Ge) or their oxide and alloy etc. as the negative electrode active material material.The theoretical capacity density of these negative electrode active material materials is bigger than material with carbon element.Especially because the low price of siliceous particles such as Si particle or silicon oxide particle, so studied widely.
Yet the particle of these negative electrode active material materials is accompanied by to discharge and recharge change in volume can take place.Therefore, especially under the situation that the active material packed density in negative pole is big, electrolyte the situation of the electrolyte that reacts institute's necessary amounts can occur can not guaranteeing to discharge and recharge from by being extruded out positive pole, negative pole, barrier film combination and the electrode group that forms of reeling.And, using under the big situation of material of change in volume, be accompanied by and discharge and recharge reaction as active material, active material particle generation micronizing, consequently the conductivity between active material particle descends.Therefore, can not obtain sufficient charge (below, be referred to as " cycle characteristics ").
So, for example open and proposed in the 2004-349056 communique to make it in conjunction with a plurality of carbon fibers, thereby carry out the example of compound particleization to contain the metal that can form lithium alloy or semimetallic active material particle as nuclear the spy.It is reported,,, also can guarantee conductivity, keep cycle characteristics even the change in volume of active material particle has taken place according to this structure.
The electrode that rechargeable nonaqueous electrolytic battery is used (anodal, negative pole) generally is to be coated with the mixture cream paste that contains active material on as the metal forming of collector body, and drying makes.Thereby make densification by dried electrode is rolled again usually, adjust to desirable thickness.Formed mixture cream like this and stuck with paste the negative pole of layer,, generated convex-concave and destruction on the surface of mixture layer because the expansion of the active material when discharging and recharging is shunk.Especially negative pole, positive pole are being reeled with barrier film and constituting under the situation of electrode group, the mixture layer that is arranged on the inboard of collector body has been subjected to stronger compression stress when reeling.Because add the strain stress that the expansion when discharging and recharging is shunk on this face, the destruction of mixture layer becomes bigger.So significant strain has taken place in the mixture layer at negative pole.The collapse, mixture layer that such phenomenon can cause the conductive network in the mixture layer from collector body peel off, anodal and the heterogeneityization to configuration state of negative pole, the exhaustion of electrolyte etc., make cycle characteristics decline.
Summary of the invention
Thereby the present invention has relaxed the strain stress that produces owing to because of the change in volume that discharges and recharges the active material that causes in the mixture layer of negative pole, improved the rechargeable nonaqueous electrolytic battery of cycle characteristics.Non-electrolyte secondary cell of the present invention has positive pole, negative pole and the intervenient nonaqueous electrolyte that comprises the anode mixture layer.Negative pole comprise comprise can embed, the anode mixture layer of the active material of removal lithium embedded ion and support the collector body of anode mixture layer, the face of anode mixture layer with the opposed place of anode mixture layer a plurality of mixture layer expansion absorption ditches are set, collector body is exposed.According to this structure, the change in volume that produces in the mixture layer because the expansion of the active material when discharging and recharging is shunk can be absorbed by this mixture layer expansion absorption ditch, makes the raising of cycle characteristics become possibility.
Description of drawings
Fig. 1 is the profile of 1 rechargeable nonaqueous electrolytic battery according to the embodiment of the present invention.
Fig. 2 A is the partial plan of structure of representing according to the embodiment of the present invention the negative pole of 1 rechargeable nonaqueous electrolytic battery.
Fig. 2 B is the partial plan of the state after expression is finished by the charging of the negative pole shown in Fig. 2 A.
Fig. 2 C is the fragmentary cross-sectional view at the A-A of Fig. 2 A line place.
Fig. 2 D is the fragmentary cross-sectional view at the A-A of Fig. 2 B line place.
Fig. 3 A is other the partial plan of structure of representing according to the embodiment of the present invention the negative pole of 1 rechargeable nonaqueous electrolytic battery.
Fig. 3 B is the partial plan of expression by the state after the charging of the negative pole shown in Fig. 3 A.
Fig. 3 C is the fragmentary cross-sectional view at the A-A of Fig. 3 A line place.
Fig. 3 D is the fragmentary cross-sectional view at the A-A of Fig. 3 B line place.
Fig. 4 schematically represents with the part amplification profile of the structure of the negative pole of 1 rechargeable nonaqueous electrolytic battery according to the embodiment of the present invention.
Fig. 5 A is the profile of the part structure of the electrode group of representing that according to the embodiment of the present invention the coiling of 2 rechargeable nonaqueous electrolytic battery forms.
Fig. 5 B is the constructed profile after the part of Fig. 5 A is further amplified.
Fig. 5 C is the constructed profile that is illustrated in the state after the charging of anode mixture layer of Fig. 5 A.
Fig. 6 is in embodiments of the present invention 3, is used for the general structural map of the manufacturing installation of the column of formation negative electrode active material on collector body.
Fig. 7 A is to use the constructed profile of the collector body in manufacturing installation as shown in Figure 6A.
Fig. 7 B is the constructed profile when forming the 1st section of negative electrode active material column body on the collector body shown in Fig. 7 A.
Fig. 7 C is connected in Fig. 7 B, the constructed profile when the column body that forms the 2nd section.
Fig. 7 D is connected in Fig. 7 C, the constructed profile when the column body that forms the 3rd section.
The explanation of symbol
1,58 negative pole
2 positive poles
3 nonaqueous electrolytes
3A electrolyte
The 3B barrier film
4 packing rings
5 lids
6 casings
7,51 collector bodies
8 anode mixture layers
10 collector bodies
12,12A, 12B, 48 anode mixture layers
14,14C mixture layer expansion absorption ditch
14A longitudinal furrow (mixture layer expansion absorption ditch)
14B traverse furrow (mixture layer expansion absorption ditch)
16, the 16A interval
34 composite negative electrode active materials
35 siliceous particles
36 carbon nano-fibers
40 manufacturing installations
41 vacuum tanks
42 gases import pipe arrangement
43 fixed stations
45 nozzles
46 deposition unit
47 vacuum pumps
52 recesses
53 protuberances
55 columns
56A, 56B, 56C column body
57 surfaces
Embodiment
Below, for embodiments of the present invention, the limit describes with reference to the figure limit.In addition, as long as the present invention then is not limited to the following content of putting down in writing based on the essential characteristic of being put down in writing by this specification.
(execution mode 1)
Fig. 1 is the profile of 1 rechargeable nonaqueous electrolytic battery according to the embodiment of the present invention.This Coin-shaped battery has: negative pole 1, and negative pole 1 in opposite directions and the nonaqueous electrolyte 3 of the positive pole 2 of when discharge reduction lithium ion and the conductive lithium ion between negative pole 1 and anodal 2.With packing ring 4 and lid 5 negative pole 1 and positive pole 2 and nonaqueous electrolyte 3 are received in the casing 6 together.Anodal 2 is to be made of collector body 7 and the anode mixture layer 8 that contains positive active material.Negative pole 1 has collector body 10 and is arranged at its surperficial anode mixture layer (hereinafter referred to as the mixture layer) 12.
And, also can in mixture layer 12, sneak into graphite-likes such as native graphite, Delanium, expanded graphite such as flaky graphite as required; Carbon black classes such as acetylene carbon black, section's qin carbon black, channel carbon black, furnace black, dim, pyrolysismethod carbon black; Conducting fibre such as carbon fiber, metallic fiber class; Metal dust such as copper or nickel class; Conductive agents such as organic conductive material such as polyphenylene derivative.
For the material of collector body 10, can use the metal forming of stainless steel, nickel, copper, titanium etc.; The film of carbon black or electroconductive resin etc.In addition, also can use carbon, nickel, titanium etc. to implement surface treatment.
Then describe anodal 2.Anode mixture layer 8 contains the LiCoO as positive active material
2Or LiNiO
2, Li
2MnO
4, or such lithium-contained composite oxide such as the mixing of these materials or complex chemical compound.As positive active material, except above-mentioned substance, also can use by LiMPO
4The olivine-type lithium phosphate that the general formula of (M=V, Fe, Ni, Mn) is represented, by Li
2MPO
4The fluoro lithium phosphate that the general formula of F (M=V, Fe, Ni, Mn) is represented etc.And, can also usually replace the part of these lithium-containing compounds with xenogenesis unit.Can carry out surface treatment with metal oxide, lithium oxide, conductive agent etc., also can carry out hydrophobization and handle the surface.
In addition, as adhesive, can use and the identical material that is used for negative pole 1.Promptly can use PVDF, polytetrafluoroethylene, polyethylene, polypropylene, aromatic polyamide resin, polyamide, polyimides, polyamidoimide, polyacrylonitrile, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, the own ester of polyacrylic acid, polymethylacrylic acid, polymethyl methacrylate, polyethyl methacrylate, the own ester of polymethylacrylic acid, polyvinyl acetate, PVP, polyethers, polyether sulfone, hexafluoro polypropylene; butadiene-styrene rubber; carboxymethyl cellulose etc.In addition, also can use the copolymer that is selected from the material more than 2 kinds in tetrafluoroethene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene, chlorotrifluoroethylene, ethene, propylene, five fluorine propylene, fluoro methyl vinyl ether, acrylic acid, the hexadiene.Perhaps also can mix the material more than 2 kinds that use is selected from these materials.
As the material of collector body 7, can use stainless steel, aluminium (Al), titanium, carbon, electroconductive resin etc.In addition, for any one above material, also can carry out surface treatment with carbon, nickel, titanium etc.
For nonaqueous electrolyte 3, can be suitable for the electrolyte solution that in organic solvent, dissolved solute and obtained or make non-currentization of electrolyte solution and so-called " polymer dielectric " that obtain with macromolecule.For the situation of using electrolyte solution at least, preferably anodal 2 and negative pole 1 between use the barrier film (not shown) of the nonwoven fabrics that constitutes by polyethylene, polypropylene, aromatic polyamide resin, amide imide, polyphenylene sulfide, polyimides etc. or micro-porous film etc., and it be impregnated in the solution.And, also can contain thermal endurance fillers such as aluminium oxide, magnesium oxide, silica, titanium oxide on the inside or the surface of barrier film.Also can with barrier film be provided with dividually by these fillers and with electrode in the identical refractory layer that adhesive constituted that uses.
The material of nonaqueous electrolyte 3 is to consider the oxidation-reduction potential etc. of active material and select.Preferred solute as being used for nonaqueous electrolyte 3 can be suitable for LiPF
6, LiBF
4, LiClO
4, LiAlCl
4, LiSbF
6, LiSCN, LiCF
3SO
3, LiCF
3CO
2, LiAsF
6, LiB
10Cl
10, low fat aliphatic carboxylic acid's lithium, LiF, LiCl, LiBr, LiI, chloroborane lithium, two (1,2-benzenediol (2-)-O, O ') (bis (1 for lithium borate, 2-benzene diolate (2-)-O, O ') lithium borate), two (2,3-naphthalenediol (2-)-O, O ') lithium borate, two (2,2 '-'-biphenyl diphenol (2-)-O, O ') borate family, (CF such as lithium borate, two (5-fluoro-2-phenol-1-benzene sulfonic acid-O, O ') lithium borate
3SO
2)
2NLi, LiN (CF
3SO
2) (C
4F
9SO
2), (C
2F
5SO
2)
2NLi, tetraphenyl lithium borate etc. generally use the salt in lithium battery.
In addition, for the organic solvent that makes above-mentioned solute dissolving, can use ethylene carbonate, propylene carbonate, butylene carbonate, carbonic acid ethenylidene ester, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, methyl formate, methyl acetate, methyl propionate, ethyl propionate, dimethoxymethane, gamma-butyrolacton, gamma-valerolactone, 1, the 2-diethoxyethane, 1, the 2-dimethoxy-ethane, methoxy ethoxy ethane, trimethoxy-methane, oxolane, tetrahydrofuran derivatives such as 2-methyltetrahydrofuran, methyl-sulfoxide, 1, the 3-dioxolanes, the 4-methyl isophthalic acid, dioxolane derivatives such as 3-dioxolanes, formamide, acetamide, dimethyl formamide, acetonitrile, propionitrile, nitromethane, glycol diethyl ether (ethyl monoglyme), phosphotriester, acetate, propionic ester, sulfolane, the 3-methyl sulfolane, 1,3-dimethyl-2-imidazolone, 3-methyl-2-azolactone, the polypropylene carbonate ester derivant, ether, diethyl ether, 1, the 3-N-morpholinopropanesulfonic acid lactone, methyl phenyl ethers anisole, mixture more than a kind or a kind such as fluorobenzene etc. generally is used in the solvent in the lithium battery.
And, also can contain vinylene carbonate, cyclohexyl benzene, biphenyl, diphenyl ether, ethylene thiazolinyl ethyl, carbonic acid divinyl ethyl, carbonic acid phenyl ethyl, carbonic acid diallyl ester, carbonic acid fluoro ethyl, carbonic acid catechol ester, vinylacetate, thiirane, propane sultone, the inferior propyl ester of carbonic acid trifluoro, dibenzofuran, 2, additives such as 4-difluoro-benzene methyl ether, ortho-terphenyl, meta-terphenyl.
In addition, nonaqueous electrolyte 3 can be above-mentioned solute is mixed or to be dissolved in that the polyelectrolyte as solid, shaped uses in a kind of of following macromolecular material or more than one the mixture, and these macromolecular materials have: polyethylene glycol oxide, PPOX, polyphosphazene, polyethylene imine, poly-thiirane, polyvinyl alcohol, Kynoar, polyhexafluoropropylene etc.And, also the polyelectrolyte of solid, shaped can be mixed the back with above-mentioned organic solvent and use with gel state.In addition, also can form by lithium nitride, lithium halide, the oxysalt of lithium, Li
4SiO
4, Li
4SiO
4-LiI-LiOH, Li
3PO
4-Li
4SiO
4, Li
2SiS
3, Li
3PO
4-Li
2S-SiS
2, the solid electrolyte that constitutes of inorganic material such as phosphoric sulfide compound and using.
Secondly, the structure of the negative pole 1 of present embodiment and the variation when discharging and recharging are described.Fig. 2 A~Fig. 2 D is the figure of structure of the negative pole of the rechargeable nonaqueous electrolytic battery of expression in the embodiments of the present invention 1.Fig. 2 A is the plane graph of the part of the negative pole before the charging, and Fig. 2 C is the profile in the part at the A-A of Fig. 2 A line place.And Fig. 2 B is the plane graph of the part of the negative pole after charging is finished, and Fig. 2 D is the profile in the part at the A-A of Fig. 2 B line place.After discharge was finished, mixture layer 12 roughly turned back to the state shown in Fig. 2 A, Fig. 2 C from state shown in Fig. 2 B, Fig. 2 D.
Shown in Fig. 2 A~Fig. 2 D, at least one surface of collector body 10, the surface combination that is coated on material has the mixture layer 12 of carbon nano-fiber (hereinafter referred to as " CNF ").For mixture layer 12, expose in order to make collector body 10, be provided with a plurality of parallel mixture layer expansion absorption ditches (hereinafter referred to as " ditch "), thereby be divided into a plurality of interval 16.Ditch 14 is arranged on and anode mixture layer 8 opposed place.
In the mixture layer 12 that is configured like this, when charging shown in Fig. 2 D, expand respectively in each interval 16 of the mixture layer of being divided by ditch 14 12.Yet for this structure, ditch 14 can absorb the variation of its volume.When charging is finished the surface portion of mixture layer 12 to adjacent each interval 16 near or become the state that connects.That is, can avoid making the integral body generation strain of mixture layer 12, thereby perhaps produce concavo-convex the fluctuating on the surface owing to the compression stress that the volumetric expansion that is accompanied by each interval 16 brings.That is, ditch 14 can be alleviated the strain that the mixture layer 12 that causes is shunk in the expansion of the active material owing to discharging and recharging.Thus, can prevent in the mixture layer 12 the crumbling of conductive network, mixture layer 12 from collector body 10 peel off, anodal 2 with negative pole 1 under configuration state, the especially charged state to the heterogeneityization of configuration state etc.And, can expect additional ditch as the electrolyte that has reduced owing to the expansion of mixture layer 12.
In addition, in Fig. 2 A~Fig. 2 D, only the single face at collector body 10 is provided with mixture layer 12, but also can be provided with on the two sides, as described later, according to the structure of battery, also can on a face ditch 14 be set.
Be provided with mixture layer 12, can embed, under the situation of the material of removal lithium embedded ion, can bring into play its effect significantly containing as the ditch 14 of the feature of present embodiment.That is, by containing the negative pole that the mixture layer of material with carbon element as active material constitutes, because the change in volume when charging is little, the effect of the mitigation stress that is produced by ditch 14 is little.And the reaction potential of material with carbon element and lithium ion only exceeds several 10mV with respect to the dissolving deposition potential of lithium metal.Therefore, if because reaction impedance produces polarization, then local potential can become below the 0V sometimes, precipitating metal lithium on collector body 10.Therefore, for the mixture layer of such negative pole, if form the ditch 14 that collector body 10 is exposed, then lithium metal is separated out easily, and the decline of cycle characteristics is also big.Because relatively significantly, the electric current when therefore wishing charging diminishes this phenomenon under the big situation of the current value in when charging.
On the other hand, the change in volume that contains when charging is big slightly but have the mixture layer of active material of the high capacity density of siliceous particle etc., with the reaction potential of lithium ion up to hundreds of mV, even the polarization that produces owing to reaction impedance takes place, local potential also is not easy to become below the 0V.Therefore, by ditch 14 is set, the expansion that can absorb mixture layer 12 is shunk, and can suppress lithium metal separating out on collector body simultaneously, makes the raising of seeking cycle characteristics become possibility.
As have such reaction potential and can embed in large quantities, the material of removal lithium embedded ion, can list is material more than 1.2 at the volume A under the charged state with respect to the ratio A/B of the volume B under discharge condition as silicon (Si) or tin (Sn) etc.Such material because capacity density is big, goes far towards the high-energy-densityization of rechargeable nonaqueous electrolytic battery.And, because it is big to expand under charged state, so can bring into play the effect of mixture layer expansion absorption ditch significantly.Siliceous particle be since discharge and recharge volumetric expansion big, have an exemplary of the above-mentioned active material of high capacity density.
So long as such material, can be simple substance, alloy, compound, solid solution and contain material or the composite reactive material of tin-containing material in any, effect of the present invention is brought into play.That is,, can use Si, SiO as material
x(0.05<x<1.95) or any usefulness that will be wherein are selected from alloy or compound or the solid solution etc. that a part of rear substitution that at least a above unit among B, Mg, Ni, Ti, Mo, Co, Ca, Cr, Cu, Fe, Mn, Nb, Ta, V, W, Zn, C, N, the Sn usually replaces Si obtains.As arsenic material, can use Ni
2Sn
4, Mg
2Sn, SnO
x(0<x<2), SnO
2, SnSiO
3, LiSnO etc.
These materials can constitute active material individually, perhaps also can be to constitute active material by multiple material.As the example that constitutes active material by above-mentioned multiple material, can list and contain Si and oxygen with nitrogen compound or contain compound of the Si a plurality of compounds different etc. with the component ratio of oxygen, Si and oxygen.Wherein, SiO
xExpansion rate during the big and charging of the discharge capacity density of (0.05<x<1.95) is littler than Si simple substance, is preferred therefore.
In order to make ditch 14 can absorb the change in volume that the mixture layer 12 that causes is shunk in the expansion owing to discharging and recharging, ditch 14 is exposed on collector body 10.Only be the ditch that makes the thickness attenuation of mixture layer 12, can not remove the strain that the change in volume owing to mixture layer 12 causes.In addition, the width of ditch 14 and be provided with ditch 14 the interval, be the OK range of shape in the interval 16 of mixture layer 12, mainly depend on the thickness of mixture layer 12.For example, as general structure, the thickness of mixture layer 12 be one-sidedly be about 70 μ m, the winding diameter of electrode group is under the situation about 18mm, need make the width of ditch 14 be 0.2mm~3mm, be spaced apart 12mm~56mm.In addition, for example can use the rod of the diameter PTFE system identical with the width of ditch 14, with the interval of regulation with a part of linearity of mixture layer 12 peel off, thereby ditch 14 is set.
For the multiple selection of being configured with of ditch 14, no matter any structure so long as be provided with ditch 14, can reach effect of the present invention.In addition, shown in Fig. 2 A~Fig. 2 D, preferably mixture layer 12 is divided into a plurality of interval 16 by ditch 14.According to this structure, make the isotropism of volumetric expansion of mixture layer 12 uprise, because mixture layer 12 does not expand at random direction, make strain become littler.
Secondly, other structure to mixture layer expansion absorption ditch describes.Fig. 3 A~Fig. 3 D is the figure of other structure of negative pole of the rechargeable nonaqueous electrolytic battery of expression embodiments of the present invention 1.Fig. 3 A is the plane graph of the part of the negative pole before the expression charging.In addition, Fig. 3 B is the plane graph of the part of the negative pole after charging is finished, and Fig. 3 D is the profile in the part at the A-A of Fig. 3 B line place.Fig. 3 C is that its section shape is same with Fig. 2 C, Fig. 2 D at the profile of the part at the A-A of Fig. 3 A line place.
As shown in Figure 3A, in this structure, be provided as the longitudinal furrow 14A of mixture layer expansion absorption ditch with respect to collector body 10 for longitudinal direction ground, and be provided as the traverse furrow 14B of mixture layer expansion absorption ditch, many and intersections mutually are set respectively at the transverse direction of collector body 10.Therefore, each interval 16A of anode mixture layer (hereinafter referred to as " mixture layer ") 12A has the square shape that is surrounded by longitudinal furrow 14A and traverse furrow 14B.After discharge was finished, mixture layer 12A roughly turned back to the state shown in Fig. 3 A, Fig. 3 C from the state shown in Fig. 3 B, Fig. 3 D.In addition, the essential structure of the rechargeable nonaqueous electrolytic battery of this structure is identical with Fig. 1.
In this structure, the shape of each interval 16A can be that rectangle also can be a square.Shown in the profile of the plane graph of Fig. 3 B and Fig. 3 D, under the dilated situation of each interval 16A of mixture layer 12A after charging is finished, the top top of each adjacent interval 16A becomes approaching or the state that connects after expanding, and the dilation of each interval 16A is absorbed by longitudinal furrow 14A and traverse furrow 14B.
In addition, the flat shape that is divided into the mixture layer 12A of a plurality of interval 16A by ditch 14A, 14B is not limited to above-mentioned shape.So long as the shape that the ditch of the change in volume that is caused by expansion contraction that can absorb the mixture layer 12A owing to discharging and recharging etc. surrounds, then limit shape not can obtain the effect that present embodiment produces.That is, with respect to the Width of negative pole 1, ditch 14A and ditch 14B promptly be not parallel neither be vertical, become inclination and also be fine.Perhaps, also can be curve-like.
In this structure, the width of ditch 14A and ditch 14B and proper range at interval mainly depend on the thickness of mixture layer 12A.For example the diameter that is about 70 μ m, electrode group at mixture layer 12A is about under the situation of 18mm, and the width of preferred ditch 14A, 14B is 0.2mm~3mm, be spaced apart 12mm~56mm.
And the interval that ditch 14A, 14B are set needs not to be equally spaced.Because near the effect that is accompanied by the compression stress volume core that curvature is high when the electrode group is reeled of change in volume of the mixture layer 12A when discharging and recharging is the strongest, can only near this volume core, ditch 14A, 14B be set partly.Perhaps also can make the interval that ditch 14A, 14B are set little, this be enlarged at interval to peripheral part at the volume core.
Secondly, the structure for preferred negative electrode active material that is used for mixture layer 12A and negative pole 1 describes.Fig. 4 is the constructed profile that the part of negative pole 1 is amplified in expression.The mixture layer 12A that has ditch 14A on the surface of collector body 10 and be provided with, comprise composite negative electrode active material (hereinafter referred to as " complex ") 34, its have as can embed, the siliceous element material or the siliceous particle 35 of the active material of removal lithium embedded ion and be attached to carbon nano-fiber (CNF) 36 on the siliceous particle 35.CNF36 is that the catalyst elements (not shown) that supported with the surface of siliceous particle 35 is grown as nuclear and formed.As catalyst elements, can use to be selected from least a among Cu, Fe, Co, Ni, Mo and the Mn, promote the growth of CNF36.In addition, as substituting of aforesaid siliceous particle 35, also can use can embed in a large number, removal lithium embedded ion and the volume A under charged state be that material more than 1.2 is as active material with respect to the ratio A/B of the volume B under the discharge condition.
The CNF36 of the fibre length with 1nm~1mm is extended on surface at mixture layer 12A.Complex 34 is to react with lithium under than the taller current potential of the deposition potential of lithium.Therefore, as long as make the current value when charging suitable, then lithium ion is difficult to directly arrive the face that exposes of collector body 10.Therefore, having suppressed lithium metal is dendroid and separates out at the face that exposes of collector body 10.
Then complex 34 is described in detail.CNF36 is the surface of adhering to or be bonded to siliceous particle 35 by the catalyst elements of the starting point that becomes its growth, and the impedance for current collection in the battery diminishes, and can keep high conductivity.And, making by catalyst elements under CNF36 and the situation that siliceous particle 35 combines, CNF36 is difficult to break away from from siliceous particle 35, is preferred.Catalyst elements has promoted consequently, can further strengthen siliceous particle 35 conductive network each other in the growth as the CNF36 on the surface of the siliceous particle 35 of active material.
So, make conductivity improve, therefore the rechargeable nonaqueous electrolytic battery that can constitute high power capacity, practicality and have the favorable charge-discharge characteristic by making CNF36 be attached to the surface of siliceous particle 35.And, the intervention of catalyst elements strengthens to the adhesion of siliceous particle 35 because making, when mixture layer 12A is set on collector body 10, can improve the durability with respect to the negative pole of calendering load, described calendering load is the mechanical load that puts on for the packed density that improves mixture layer 12A on the mixture layer 12A.
, during stopping,, be preferably catalyst elements and exist with metallic state in the growth of CNF36 in the skin section of siliceous particle 35 in order to make the good catalytic action of catalyst elements performance.The catalyst elements preference is as being that the state of the metallic of 1nm~1000nm exists with the particle diameter.On the other hand, after the growth of CNF36 stops, the preferably metallic oxidation that will constitute by catalyst elements.
The fibre length of CNF36 is preferably 1nm~1mm, more preferably 500nm~100 μ m.When the not enough 1nm of the fibre length of CNF36, the effect that improves the conductivity of electrode can become too small, and when fibre length during above 1mm, the density of active material and capacity have the tendency that diminishes in addition.Especially in the present embodiment, on mixture layer 12A, ditch 14A, 14B are set, the part of collector body 10 is exposed,, preferably make the fibre length of CNF36 form longer in order to suppress the contact of electrolyte 3A to collector body 10.
Form to CNF36 has no particular limits, and is preferably by at least a kind that is selected from tubulose carbon, gauffer shape carbon, sheet carbon and the herring-bone form carbon to constitute.CNF36 also can wrap into catalyst elements the inside of self in developmental process.And the fiber of CNF36 directly is preferably 1nm~1000nm, more preferably 50nm~300nm.
Catalyst elements is used to make the active site of CNF36 growth at metallic state.That is, if the siliceous particle 35 of catalyst elements with the metallic state exposing surface imported in the high-temperature atmosphere of the unstrpped gas that contains CNF36, then CNF36 begins growth.For the situation that does not have catalyst elements on the surface of active material particle, CNF36 does not grow.
Method for the metallic that is made of catalyst elements is set on the surface of siliceous particle 35 has no particular limits, and for example suitable is in the method for the surperficial carrying metal particle of siliceous particle 35 etc.
Under situation, the metallic of solid can be mixed with siliceous particle 35 with said method carrying metal particle.And, be preferably the method for the siliceous particle 35 of dipping in as the metal compound solution of the raw material of metallic.Remove the siliceous particle 35 after being immersed in solution and desolvate, carry out heat treated as required, then can obtain the surface and support by particle diameter evenly and with high dispersion state and be 1nm~1000nm, be preferably the siliceous particle 35 of the metallic that the catalyst elements of 10nm~100nm constitutes.
Under the situation of particle diameter less than 1nm of the metallic that is made of catalyst elements, the generation of metallic is difficulty very.In addition, when surpassing 1000nm, the extreme heterogeneity that the size of metallic becomes becomes sometimes and is difficult to make the CNF36 growth, maybe can not obtain high conductive electrode.Therefore, the particle diameter of the metallic that is made of catalyst elements is preferably below the above 1000nm of 1nm.
As the metallic compound that is used to modulate above-mentioned solution, can list nickel nitrate, cobalt nitrate, ferric nitrate, copper nitrate, manganese nitrate, seven molybdic acids, six ammonium tetrahydrates etc.In addition, for the solvent that is used for solution, can consider with the solubility of compound, with electro-chemical activity adaptability mutually, from the mixture of water, organic solvent and water and organic solvent, suitably select.The implication of electro-chemical activity phase is meant: the crystalline phase that constitutes siliceous particle 35 or noncrystalline mutually in, the redox reaction that can follow electron transfer is that metal phase, the metal oxide of cell reaction equates crystalline phase or noncrystalline phase.As organic solvent, can use for example ethanol, isopropyl alcohol, toluene, benzene, hexane, oxolane etc.
On the other hand, also can synthesize the alloy particle that contains catalyst elements, it is used as siliceous particle 35.In this case, the alloy of Si and catalyst elements is synthetic with common alloy manufacture method.Generate alloy because of Si element and lithium generation electrochemical reaction, so form the electro-chemical activity phase.On the other hand, at least a portion of the metal phase that is made of catalyst elements for example is that the particle shape of 10nm~100nm exposes the surface at alloy particle with the particle diameter.
0.01 weight %~10 weight % that metallic that is made of catalyst elements or metal are preferably siliceous particle 35 mutually, more preferably 1 weight %~3 weight %.If the content of metallic or metal phase is very few, then in order to make the CNF36 growth needs long-time, the low situation of production efficiency can appear.On the other hand, if the content of metallic that is made of catalyst elements or metal phase is too much,, cause the conductivity in the mixture layer or the reduction of active material density then because the cohesion of catalyst elements can grow into CNF36 inhomogeneous and the crude fibre diameter.And the ratio of electro-chemical activity phase tails off relatively, is difficult to complex 34 is made the electrode material of high power capacity.
Secondly, the manufacture method of the complex 34 that is made of siliceous particle 35 and CNF36 is narrated.This manufacture method is made of 4 following steps.
(a) can embed, the surface element at least of the siliceous particle 35 of removal lithium embedded is provided with the step that is selected from least a catalyst elements among Cu, Fe, Co, Ni, Mo and the Mn that promotes the CNF36 growth.
(b) in the atmosphere that contains carbonaceous gas and hydrogen, make the step of CNF36 growth on the surface of siliceous particle 35.
(c) in torpescence atmosphere, 400 ℃~1600 ℃ steps of firing the siliceous particle 35 that has adhered to CNF36.
(d) the siliceous particle 35 that has adhered to CNF36 is pulverized, tap density is adjusted into 0.42g/cm
3~0.91g/cm
3Step.
After step (c), also can be further in atmosphere, complex 34 be carried out 100 ℃~400 ℃ heat treatment, so that the catalyst elements oxidation.So long as 100 ℃~400 ℃ heat treatment, then can make CNF36 not oxidized and have only catalyst elements oxidized.
As step (a), the alloy particle of method, synthetic Si element and the catalyst elements of can list the method that supports the metallic that constitutes by catalyst elements on the surface of siliceous particle 35, the surface of the siliceous particle 35 that contains catalyst elements being reduced etc.But step (a) is not limited only to said method.
Secondly, in step (b), the condition when making the CNF36 growth for the surface at siliceous particle 35 describes.When will be at least when the siliceous particle 35 that skin section has a catalyst elements imports in the high-temperature atmosphere of the unstrpped gas that contains CNF36, the growth of CNF36 has just begun.For example drop into siliceous particle 35, at inactive gas or have in the gas of reducing power and be warming up to 100 ℃~1000 ℃, be preferably 300 ℃~600 ℃ high temperature to the ceramic reaction vessel.Afterwards, will import reaction vessel as the carbonaceous gas and the hydrogen of the unstrpped gas of CNF36.When 100 ℃ of temperature less thaies in the reaction vessel, the growth of CNF36 does not take place, perhaps growing impairs productivity slowly.In addition, when the temperature in the reaction vessel surpasses 1000 ℃, then quickened the decomposition of unstrpped gas, made the growth of CNF36 become difficult.
As unstrpped gas, the mist of carbonaceous gas and hydrogen suits.As carbonaceous gas, can use methane, ethane, ethene, butane, CO etc.In mist, the mol ratio of carbonaceous gas (volume ratio) is preferably 20%~80%.For the situation of not exposing the catalyst elements of metal shape on the surface of siliceous particle 35, be more by the ratio of controlling hydrogen, can carry out the reduction of catalyst elements and the growth of CNF36 simultaneously.For the growth that makes CNF36 stops, the mist of carbonaceous gas and hydrogen is replaced into inactive gas, will be cooled to room temperature in the reaction vessel.
In addition, as siliceous particle 35, by using by SiO
xThe silicon oxide particle of the compositing range shown in (0.05<x<1.95) is easy to make CNF36 to be attached to the surface of siliceous particle 35.
Then, by step (c), the siliceous particle 35 that has adhered to CNF36 is fired in 400 ℃~1600 ℃ under inertness atmosphere.By doing like this, electrolyte that the initial stage charging of battery the time carries out and the irreversible reaction of CNF36 are suppressed, can access good efficiency for charge-discharge, be preferred therefore.Be not lower than 400 ℃ if do not carry out such ablating work procedure or firing temperature, then can not suppress above-mentioned irreversible reaction, the efficiency for charge-discharge of battery is reduced.In addition, if firing temperature surpasses 1600 ℃, the electro-chemical activity of then siliceous particle 35 mutually and CNF36 react, make the electro-chemical activity deactivation that becomes mutually, perhaps electro-chemical activity is reduced mutually, thereby causes capacity decline.For example, be the situation of Si mutually for the electro-chemical activity of siliceous particle 35, Si and CNF36 react and have generated the carborundum of inertia, have caused the decline of the charge/discharge capacity of battery.In addition, be the situation of Si for siliceous particle 35, preferred especially firing temperature is 1000 ℃~1600 ℃.In addition, can improve the crystallinity of CNF36 according to growth conditions.For the high situation of the crystallinity of CNF36, because also can suppress the irreversible reaction of electrolyte and CNF36, so step (c) just not necessarily like this.
In step (d), the siliceous particle 35 that has adhered to CNF36 after the calcining is pulverized.By doing like this, can access the good complex of fillibility 34, so be preferred.But even if do not pulverize, tap density also is 0.42g/cm
3~0.91g/cm
3Situation, just do not have the necessity that must pulverize.That is, using under the good situation of siliceous particle of fillibility, the situation about pulverizing of not needing is also being arranged as raw material.
In addition, complex 34 also can be suitable for the structure shown in Fig. 2 A~Fig. 2 D.
Fig. 5 A is illustrated in the execution mode 2, to anodal, negative pole is reeled and the profile of the structure of the part of the rechargeable nonaqueous electrolytic battery that constitutes.Fig. 5 B, what Fig. 5 C represented is further to amplify the wherein constructed profile of a part.Fig. 5 B represents discharge condition respectively, and Fig. 5 C represents charged state.The rechargeable nonaqueous electrolytic battery of present embodiment has reels negative pole 1 and anodal 2 and the electrode group of formation across barrier film 3B.In addition, though omitted anodal 2 detailed construction, for the structure of mixture layer is set on the two sides of collector body.
Shown in Fig. 5 A, be respectively arranged with anode mixture layer (hereinafter referred to as " mixture layer ") 12B, 48 on the two sides of the collector body 10 that constitutes by Cu paper tinsel etc.Mixture layer 12B for the interior all sides at the coiling direction of electrode group are provided with is provided with a plurality of mixture layer expansion absorption ditches (hereinafter referred to as " ditch ") 14C.Ditch 14C is set at and the opposed place of anode mixture layer.Shown in Fig. 5 B, Fig. 5 C, mixture layer 12B in the present embodiment contains the complex 34 of explanation in execution mode 1.
Shown in Fig. 5 C, though when charging mixture layer 12B each interval taken place owing to the change in volume that can embed, the expansion of the siliceous particle 35 of the active material of removal lithium embedded ion causes, the volume of its expansion is absorbed by ditch 14C.Therefore, shrink the compression stress that causes and obtain relaxing, can prevent generation at the ess-strain on the surface of mixture layer 12B etc. owing to the expansion in each interval.Owing to suppressed such strain, prevented in mixture layer 12B the crumbling of conductive network, mixture layer 12B from collector body 10 peel off, anodal 2 and negative pole 1 to the heterogeneityization of configuration state etc., improved cycle characteristics.In addition, if all sides are provided with ditch 14C in the high coiling of curvature, the initial stage strain that the compression stress of the upper surface of the mixture layer 12B that produces during then owing to coiling causes also can be absorbed by ditch 14C, can further relax the stress that the volumetric expansion owing to discharging and recharging causes, be preferred therefore.
In addition, more preferably ditch 14C substantially is provided with perpendicular to the coiling direction of negative pole 1.According to this structure, the initial stage strain that the compression stress of the upper surface of the mixture layer 12B that produces in the time of can alleviating owing to coiling effectively causes.
In addition, it is against each other that each interval of mixture layer 12B is preferably the upper surface end in its outer surface end and adjacent interval.The surface of the collector body 10 that exposes by ditch 14C is blocked by the upper surface between adjacent region, has suppressed lithium ion thus and has immersed to the surface of collector body 10, can reduce lithium metal separating out on collector body 10.And, because can with across the subtend face of barrier film 3B opposed anodal 2 as continuous anode mixture layer, therefore can improve anodal 2 reaction efficiency.
Shown in Fig. 5 B, extend the CNF36 of fibre length with 1nm~1mm on the surface of mixture layer 12B.Because the end of each interval outer surface of CNF36 and mixture layer 12B connects, and lumps together so intricately twines.In this case, also situation about representing with Fig. 4 is identical, and the lithium ion that is contained among the electrolyte 3A can not immerse in the ditch 14C, has suppressed lithium and has separated out to the face that exposes of collector body 10.In addition, CNF36 becomes feeler, will be connected by the mixture layer 12B that ditch 14C is distinguished.This CNF36 connection has to each other improved the conductivity of mixture layer 12B.
In addition, it is narrow more at interval that ditch 14C preferably is set to when making the electrode group approaching more volume core.Thus, can also prevent to roll up the generation of the ess-strain of core when reeling effectively.And, in the above explanation, although understand the situation of in negative pole 1, having used complex 34, but under situation about containing at least, be effective as the material of can the embedding of active material, removal lithium embedded ion.
And, as in the general employed graphite of negative electrode active material etc., because charging has 20% to expand approximately.Therefore,, preferably mixture layer expansion absorption ditch 14C is arranged on the interior all sides when collector body 10 is reeled at least among the mixture layer 12B, and the current value during to charging is optimized for the situation of filling negative electrode active material to high-density.Can improve cycle characteristics thus.Certainly, also be identical at the mixture that uses material and graphite etc. under as the situation of negative electrode active material.
Then, the specific embodiment in the present embodiment is described.In addition, though present embodiment is that coiled cylindrical shape secondary cell is described, the shape of battery of the present invention is not limited to cylindrical shape, also can be suitable for for the Coin-shaped battery of plate shaped battery, coiled rectangular cell or lit-par-lit structure.
(1) Zheng Ji making
With respect to LiNi as positive active material
0.8Co
0.17Al
0.03O
2100 weight portions, mix as acetylene black 3 weight portions of conductive agent, as the PVDF4 weight portion of adhesive, evenly disperse N-methyl pyrrolidone (NMP) as solvent, be modulated into cream and stick with paste.
This cream muddle is distributed in aluminium (Al) paper tinsel of thick 15 μ m, and calendering makes that the density of mixture layer is that 3.5g/cc, thickness are 160 μ m.It is cut off with wide 57mm, long 600mm, make anodal 2.Interior all sides anodal 2 with negative pole 1 exposed division of 30mm, the positive wire of welding Al system are not set on the aluminium foil of opposed position.
(2) making of negative pole
As can embed, the siliceous particle 35 of the active material of removal lithium embedded ion, in the present embodiment, having used particle diameter after pulverizing is that the following and O/Si of 10 μ m is than the silica (SiO that is 1.01 with molar ratio computing
1.01).
In addition, be incorporated into the skin section of this silicon oxide particle, use ferric nitrate 9 hydrates (superfine) 1g to be dissolved in ion exchange water 100g and the solution that obtains in order to make catalyst elements.In addition, to be based on JIS Z2613 be that benchmark carries out with the gravimetry to the mensuration of the mol ratio of silicon oxide particle.After the mixture of this silicon oxide particle and iron nitrate solution stirred 1 hour, by removing moisture, thus at the skin section homogeneous of silicon oxide particle and to have supported particle diameter with high dispersion state be the ferric nitrate of 1nm~1000nm with vaporising device.
Secondly, the siliceous particle 35 that has supported this ferric nitrate is put in the reaction vessel of ceramic, in the presence of helium, be warming up to 500 ℃.Afterwards, it is that 50% volume and carbon monoxide are the mist of 50% volume that helium replacement is become hydrogen, keeps 1 hour at 500 ℃.Thus, in the reduction ferric nitrate, in the superficial growth of siliceous particle fibre diameter be about the flat CNF36 that 80nm, fibre length are about 50 μ m.
Secondly, again mist is replaced as helium, makes the reaction vessel interior cool to room temperature.The amount of the CNF36 of growth is 30 weight portions with respect to the siliceous particle of per 100 weight portions.So modulated complex 34.
Then, stick with paste in order to make cream, 100 weight portions with respect to complex 34, to be 150,000 polyacrylic acid 1% aqueous solution as the mean molecule quantity of adhesive to be scaled solid and to be divided into 10 weight portions and core sheath (core shell) type modification butadiene one styrol copolymer 10 weight portions mix, add distilled water 200 weight portions then and mix dispersion, be modulated into cathode agent cream and stick with paste.With this cathode agent cream stick with paste by scrape the skill in using a kitchen knife in cookery be coated on by thick be the two sides of the collector body 10 that constitutes of the Cu paper tinsel of 14 μ m, drying makes dried gross thickness (comprising the Cu paper tinsel) become 148 μ m, thereby forms mixture layer 12B, 48.Afterwards, carrying out roll-in prolongs and adjusts mixture layer 12B, 48 thickness.
So, the two sided coatings at collector body 10 being had the negative pole non-individual body of mixture layer 12B, 48 band shape, is that 59mm, length are that the size of 750mm is cut off with wide.
Secondly, on mixture layer 12B,, make collector body 10 expose forming the ditch 14C of the linearity of the wide 2mm of being at interval with 20mm with the almost vertical direction of coiling direction.End at collector body 10 is provided with the wide exposed division of 5mm that is then, welds the cathode conductor of nickel (Ni) system here.
(3) making of battery
Electrode group with making as mentioned above is immersed in 1.0mol/dm
3LiPF
6Be dissolved in by ethylene carbonate (EC): dimethyl carbonate (DMC): in the mixed solvent that methyl ethyl carbonate (EMC)=2: 3: 3 (volume ratio) constitutes and in the electrolyte that obtains,, to 3.5V, decompose the electrode group and also take out negative pole 1 with the constant current charge of 300mA.
This electrode group is inserted the only cylinder battery casing (material: iron/Ni plating of one-sided opening, diameter is 18mm, the high 65mm of being), between casing and electrode group, dispose insulation board, behind welding cathode conductor and the casing, welding positive wire and hush panel, thus battery made.
After 60 ℃ of these batteries of heating make its drying in a vacuum, inject 5.8g with 1.0mol/dm
3LiPF
6Be dissolved in by EC: DMC: EMC=2: in the mixed solvent that 3: 3 (volume ratio) constitutes and the electrolyte that obtains is sealed up hush panel to casing and made it airtight.
The battery that making like this is obtained, carrying out 3 end of charge voltage repeatedly with the constant current of 300mA is that 4.1V, final discharging voltage are discharging and recharging of 2.0V, makes the rechargeable nonaqueous electrolytic battery of the theoretical capacity that has possessed 3000mA.With this as embodiment 1.
(embodiment 2)
Except as shown in Figure 3A will ditch that mixture layer 12B is provided with as clathrate, other and embodiment 1 constitute battery in the same manner, with it as embodiment 2.
(embodiment 3,4)
Except will becoming 3mm and 0.2mm at the width of the ditch 14C that mixture layer 12B is provided with, other and embodiment 1 constitute battery in the same manner, with it respectively as embodiment 3,4.
(comparative example 1,2)
Except the two sides at negative pole 1 was not provided with ditch in anode mixture layer, other and embodiment 1 constituted battery in the same manner, with its as a comparative example 1; Except the degree of depth that makes ditch form mixture layer (one-sided) thickness half, do not make collector body 10 exposes, other and embodiment 1 constitute battery in the same manner, with its as a comparative example 2.
(embodiment 5)
Mixing is stuck with paste thereby make cream as graphite 100 weight portions of negative electrode active material, as butadiene-styrene rubber 3 weight portions of adhesive, as the carboxymethyl cellulose aqueous solution of tackifier and make its solid be divided into 1 weight portion.It is coated the Cu paper tinsel, and calendering makes that the packed density of the active material (graphite) among the mixture layer 12B of per unit volume is 1.7g/cm
3, thickness is 183 μ m, cuts off into the wide 59mm of being then, longly is 698mm, constitutes battery in the same manner with embodiment 1 in addition, with it as embodiment 5.
(embodiment 6)
Except the packed density of the active material (graphite) among the mixture layer 12B that makes per unit volume becomes 1.6g/cm
3In addition, other and embodiment 5 constitute battery in the same manner, with it as embodiment 6.
(comparative example 3)
Except the two sides at negative pole was not provided with ditch in anode mixture layer, other and embodiment 5 constituted battery in the same manner, with its as a comparative example 3.
(comparative example 4)
Except the two sides at negative pole was not provided with ditch in anode mixture layer, other and embodiment 6 constituted battery in the same manner, with its as a comparative example 4.
Each battery for as above constituting has carried out evaluation as follows.
(cycle characteristics)
For embodiment 1~4, comparative example 1,2,2A charges to 4.2V with maximum current, has carried out keeping the voltage of 4.2V that the constant voltage of current value decay is charged.In addition, for embodiment 5,6 and comparative example 3,4,1A charges to 4.2V with maximum current, has carried out keeping the voltage of 4.2V that the constant voltage of current value decay is charged.Both be charged to decay current under every kind of situation and become 0.3A.Then, constant current discharge to the voltage with 3A becomes 2V.Under these conditions, discharge and recharge repeatedly, the period that discharge capacity is dropped to respect to the capacity of the 1st circulation at 70% o'clock is as the index of cycle characteristics.
(visual examination of electrode group and negative pole)
With above-mentioned cycle characteristics evaluation in discharge and recharge repeatedly under the identical condition, divide electrolytic cell at the 150th circulation time, confirm that the electrode group has or not distortion.The situation of certifiable distortion is designated as " the electrode group has distortion " with estimating as can be seen, otherwise is " nothing ".And, observed the electrode group from top.Be provided with ditch 14C a side (inboard) mixture layer 12B adjacent interval in enclose end face each other the situation of butt be designated as " interval butt ", otherwise be " nothing ".
Again the electrode group is decomposed, negative pole 1 is recovered smooth, confirm that the mixture layer has or not distortion.The situation that can obviously find out identifiable gauffer is designated as " negative pole has gauffer ", has the situation in some fine cracks to be designated as " having ", being designated as of non-above-mentioned situation " nothing ".
At first each specification and the evaluation result with embodiment 1~4, comparative example 1,2 is shown in table 1.
Table 1
Ditch | Interval butt | Capacity is kept 70% period | The distortion of electrode group | The gauffer of negative pole produces | ||
Copper Foil exposes | Furrow width (mm) | |||||
|
Have | 2 | Have | 350 | Do not have | Do not have |
|
Have | 2 | Have | 360 | Do not have | Do not have |
|
Have | 3 | Do not have | 290 | Do not have | Do not have |
|
Have | 0.2 | Have | 320 | Do not have | Have |
Comparative example 1 | Do not have | - | - | 150 | Have | Have |
Comparative example 2 | Do not have | 2 | Do not have | 220 | Have | Have |
In the comparative example 1 that ditch is not set, can see the distortion of significant electrode group.Can think that this is because not to because the function that the change in volume of the mixture layer that causes absorbs is shunk in the expansion of mixture layer, so the negative pole distortion, produce gauffer and it causes with the form of putting aside.
In addition, can think this phenomenon can cause the crumbling of conductive network in the mixture layer, mixture layer from collector body 10 peel off, positive pole and negative pole to heterogeneityization of configuration state etc., relevant with the decline of cycle characteristics.In addition, though comparative example 2 is provided with ditch, owing to do not reach the degree that collector body 10 is exposed, though therefore cycle characteristics has alleviated than the comparative example 1 that does not have ditch, for practical or insufficient.
With respect to these comparative examples, formed and make the embodiment 1 of the ditch 14C that collector body 10 exposes show good cycle characteristics.Can think that the ditch 14C that is deep to collector body 10 of setting can absorb owing to expanding and shrink the change in volume of the mixture layer 12B that causes, therefore can suppress the distortion of negative pole 1 and electrode group.
And can think because between the adjacent region of mixture layer 12B in enclose end face butt each other, so lithium do not separate out at the exposed division of collector body 10, this is also relevant with the raising of cycle characteristics.
The shape of ditch 14C is made cancellate embodiment 2 with respect to embodiment 1, because can think that its function of change in volume that absorbs the mixture layer 12B of negative pole 1 has increased, though therefore little or nothing increases, cycle characteristics has just further improved.
In addition, can think that the butt that has increased end face between the adjacent region of embodiment 3 mixture layer 12B when reeling of width of ditch 14C is inadequate, and because charging current is big, therefore on collector body 10 lithium having taken place and separated out, though seldom, makes cycle characteristics have slightly and descend.
On the other hand, can think, in the situation of the embodiment 4 of the width that has dwindled ditch 14C, though the end face of the interior all sides of the coiling between the adjacent region of mixture layer 12B is butt each other, but owing to can not utilize ditch fully to absorb the change in volume of mixture layer 12B, so the too late embodiment 1 of the raising of cycle characteristics.
Next, with embodiment 5,6, each specification and the evaluation result of comparative example 3,4 are shown in table 2.
Table 2
Ditch | Packed density g/cm 3 | Capacity is kept 70% period | The distortion of electrode group | The gauffer of negative pole produces | ||
Copper Foil exposes | Furrow width (mm) | |||||
|
Have | 2 | 1.7 | 360 | Do not have | Do not have |
|
Have | 2 | 1.6 | 380 | Do not have | Do not have |
Comparative example 3 | Do not have | - | 1.7 | 300 | Do not have | Do not have |
Comparative example 4 | Do not have | - | 1.6 | 370 | Do not have | Do not have |
In embodiment 5, the comparative example 3, will be increased to 1.7g/cm as the packed density of the graphite of active material
3Be not provided with in anode mixture layer in the comparative example 3 of ditch, though do not see the distortion of electrode group, it is about 300 circulations that capacity becomes 70%.With respect to this, the embodiment 5 that is provided with ditch 14C in anode mixture layer 12B has shown excellent cycle characteristics.Can think that this is because be provided with ditch 14C, make that the electrolyte exhaustion as the main cause of cycle characteristics deterioration has obtained alleviation.
In embodiment 6, the comparative example 4, will be made as 1.6g/cm as the packed density of the graphite of active material
3In this case, the cycle characteristics that is provided with the embodiment 6 of ditch 14C in anode mixture layer 12B is compared with the cycle characteristics of the comparative example 4 that ditch is not set in anode mixture layer, does not almost have what change.Therefore, the packed density at the active material of for example graphite is 1.7g/cm
3Under the above situation, can access significant effect.
(execution mode 3)
Fig. 6 is the summary pie graph that is used on collector body forming as the manufacturing installation of the column of the silica of negative electrode active material.Manufacturing installation 40 has: thus be used for the surface sediment evaporation material of collector body 51 form column deposition unit 46, oxygen is imported the fixed station 43 that the gas in the vacuum tank imports pipe arrangement 42 and collector body 51 is fixed.These are configured in the vacuum tank 41.Reduce pressure in 47 pairs of vacuum tanks 41 of vacuum pump.Front end at gas importing pipe arrangement 42 is provided with the nozzle 45 that discharges oxygen in vacuum tank 41.Fixed station 43 is arranged at the top of nozzle 45.Deposition unit 46 is set at the vertical lower of fixed station 43.Deposition unit 46 comprises the crucible as the electron beam of heating part and configuration evaporation raw material.In manufacturing installation 40,, can change the position relation of collector body 51 and deposition unit 46 according to the angle of fixed station 43.
Secondly, use the constructed profile of Fig. 7 A~Fig. 7 D that the step that forms the column of silica on collector body 51 is described.At first, shown in Fig. 7 A, the metal forming of using copper or nickel etc. forms recess 52 and protuberance 53 on its surface with galvanoplastic as base material.Prepared for example to be formed with the collector body 51 of protuberance 53 like this with the interval of 20 μ m.Then, the fixed station of representing at Fig. 6 43 is fixed collector body 51.
Then, as shown in Figure 6, fixed station 43 is set, makes that the normal direction of collector body 51 becomes angle ω ° (for example 55 °) with respect to the incident direction from deposition unit 46.For example Si (chip silicon, purity 99.999%) is made evaporation with the electron beam heating then, and incide on the protuberance 53 of collector body 51.That is, make the direction of arrow incident of Si from Fig. 7 B.Meanwhile, import pipe arrangement 42 from gas and import oxygen (O
2), supply with to collector body 51 from nozzle 45.That is, the inside of vacuum tank 41 for example becomes that pressure is the oxygen atmosphere of 3.5Pa.Thus, with the SiO of Si and oxygen be combined into
xBe deposited on the protuberance 53 of collector body 51, form first section column body 56A of the height (thickness) of regulation, at this moment, column body 56A forms with respect to the face that protuberance 53 is not set 57 of collector body 51 angle with θ 1.
Secondly, shown in the dotted line among Fig. 6, rotation fixed station 43 makes that the normal direction of collector body 51 becomes the position of (360-ω) ° (for example 305 °) angle with respect to the incident direction from deposition unit 46.Then, from deposition unit 46 the Si evaporation and the direction of arrow from Fig. 7 C are incided on the 1st section the column body 56A of collector body 51.Simultaneously, import pipe arrangement 42 from gas and import oxygen, supply with to collector body 51 from nozzle 45.Thus, SiO
xOn first section column body 56A, form second section column body 56B of the height (thickness) of regulation with the angle of θ 2 with respect to face 57.
Secondly, fixed station 43 is turned back to the state identical with Fig. 7 B, above column body 56B, height according to the rules (thickness) forms the 3rd section column body 56C.Thus, column body 56B and column body 56C be tiltedly upright angle with oblique cube to different and making.In addition, column body 56A and column body 56C form in same direction.Thus, on collector body 51, formed the column 55 that constitutes by 3 sections column body.
Can will be like this on collector body 51, form column 55 and make the negative pole 58 that obtains and use as the substituting of negative pole 1 among Fig. 1 for example.In this case, if regard the aggregate of column 55 as anode mixture layer, then column 55 interval each other can be regarded as with the opposed local a plurality of mixture layer expansion absorption ditches that collector body 11 is exposed that are provided with of anode mixture layer 8.
In addition, in the above description,, be not limited to this though be to be that example is illustrated with the column 55 that constitutes by 3 sections column body.For example, by repeating the step of Fig. 7 B and Fig. 7 C, can form the column that constitutes by the column body of n section (n 〉=2) arbitrarily.And, oblique cube of each section of the column that constitutes by the n section to, can control with respect to the ω angle that incident direction became by the normal to a surface direction that fixed station 43 changes collector bodies 51 from deposition unit 46.
Secondly, the specific embodiment in the present embodiment is described.In addition, in the present embodiment,, use lithium metal to substitute anodal 2, be made into the Coin shape model battery identical, estimate with Fig. 1 as to electrode for the effect that makes the mixture layer expansion absorption ditch in the negative pole 58 is clear and definite.
(embodiment 7)
The banded electrolytic copper foil that uses thick 30 μ m forms protuberance 53 with galvanoplastic with interval 20 μ m on its surface, thereby has prepared collector body 51 as base material.Below, according to above-mentioned steps, adjust the angle of fixed station 43, make angle ω ° to become 60 °, having formed height with the film forming speed of about 8nm/s is 10 μ m, cross-sectional area is 300 μ m
2Column body 56A.Then, adjust the angle of fixed station 43, form column body 56B, 56C.The height that has so formed 3 sections on collector body 51 is 30 μ m, and cross-sectional area is 300 μ m
2Column 55.With collector body 51 stamping-outs is that diameter is the circle of 12.5mm, thereby has made negative pole 58.After this, thick at the surperficial evaporation of negative pole 58 by vacuum vapour deposition is the lithium metal of 15 μ m.
In addition, the section by scanning electron microscope is observed, and angle θ 1, the θ 2 with respect to the face 57 of collector body 51 of column body 56A, 56B, 56C estimated.Consequently, the tiltedly upright angle of the column body of each section is approximately 41 °.
It is 20mm, thick in the 1.6mm casing 6 that the negative pole of as above making 58 is inserted diameter.Above it across thick be the barrier film 3B configuration lithium metal of 20 μ m after, inject several electrolyte 3A, seal, be model battery about 8.8mAh thereby made theoretical capacity.Electrolyte is to EC: DMC: EMC=2: dissolved 1.0mol/dm in the mixed solvent of 3: 3 (volume ratio)
3LiPF
6And modulation obtains.
(comparative example 5)
As a comparative example 5, except using on the collector body that does not have protuberance 53 with SiO
xMake beyond the negative pole that obtains thereby be deposited as tabular, other is with having made the model battery with embodiment 7 identical manufacture methods.That is, with thick be the banded electrolytic copper foil of 30 μ m as collector body, in Fig. 6, set fixed station 43, make that the normal direction of collector body 51 becomes 180 °, in addition, deposits SiO in the same manner with embodiment 7 with respect to the incident direction from deposition unit 46
x
(evaluation of model battery)
With make like this each the model battery obtain with the constant current discharge of 0.44mA to 0V, then with the constant current charge of 0.44mA to 1V.Carry out charge and discharge cycles test, promptly so repeatedly operation drop to up to charging capacity first time charging capacity 70%.And, the model battery after the charge and discharge cycles test is decomposed, observe the state of negative pole.Evaluation result is shown in table 3.
In addition, in the present embodiment, because negative pole 58 and the lithium metal higher than lithium metal current potential are made up and the component model battery, therefore, by charging, negative pole 58 removal lithium embedded ions, by discharge, negative pole 58 embeds lithium ions.That is, become opposite with the situation of common battery.
Table 3
Ditch | Capacity is kept 70% period | The gauffer of negative pole produces | ||
Copper Foil exposes | Furrow width (mm) | |||
|
Have | 0.01 | 410 | Do not have |
Comparative example 5 | Do not have | - | 270 | Have |
Can find out obviously that as table 3 compare with comparative example 5, the charge of the model battery of embodiment 7 has significantly improved.And the negative pole 58 after the test does not produce gauffer yet.Like this, even the width of mixture layer expansion absorption ditch is 20 μ m, be 300 μ m as long as be equivalent to the cross-sectional area of the column 55 in mixture layer interval
2About, then can increase substantially charge.
On the other hand, the negative pole after the test of comparative example 5 has produced gauffer significantly.Can think that in comparative example 5, active material is set to very tight, not only in negative pole, not comprise the parts that such expansion absorbs to CNF, and not have mixture layer expansion absorption ditch, so the influence of the expansion of active material is big.
Rechargeable nonaqueous electrolytic battery among the present invention has been realized high power capacity, high load characteristics, and can improve charge significantly, therefore, can help from now on by the High Level of the raising of the life characteristic of the lithium battery of wilderness demand and energy density.
Claims (according to the modification of the 19th of treaty)
1. (revise afterwards) a kind of rechargeable nonaqueous electrolytic battery, it comprises positive pole, negative pole and the nonaqueous electrolyte between described positive pole and described negative pole, wherein,
Described positive pole comprises the anode mixture layer;
Described negative pole comprise contain can embed, the anode mixture layer of the active material of removal lithium embedded ion and support the collector body of described anode mixture layer; And the surface of described anode mixture layer with the opposed place of described anode mixture layer a plurality of mixture layer expansion absorption ditches are set, described collector body is exposed;
Described positive pole and described negative pole are reeled, the interior all sides when the described at least collector body that described mixture layer expansion absorption ditch is set at described anode mixture layer is reeled; The mutual butt in end across the outer surface of the adjacent described anode mixture layer of described mixture layer expansion absorption ditch.
2, rechargeable nonaqueous electrolytic battery according to claim 1, wherein, described anode mixture layer is divided into independently a plurality of intervals by described mixture layer expansion absorption ditch.
3, (deletion)
4, (after revising) rechargeable nonaqueous electrolytic battery according to claim 1, wherein, the coiling direction of described mixture layer expansion absorption ditch and described negative pole comes down to vertically disposed.
5, (deletion)
6, rechargeable nonaqueous electrolytic battery according to claim 1, wherein, the volume of described active material under charged state is more than 1.2 with respect to the ratio of the volume under discharge condition.
7, rechargeable nonaqueous electrolytic battery according to claim 6, wherein, described anode mixture layer further comprises: be attached to the surface of described active material carbon nano-fiber, be used for promoting at least a kind of catalyst elements that is selected from Cu, Fe, Co, Ni, Mo and Mn of the growth of described carbon nano-fiber;
Described active material and described carbon nano-fiber and described catalyst elements have formed composite negative electrode active material.
8, rechargeable nonaqueous electrolytic battery according to claim 1, wherein, described active material is a material.
9, rechargeable nonaqueous electrolytic battery according to claim 8, wherein, described material is by SiO
xThe silica of expression, 0.05<x in the formula<1.95.
Claims (9)
1. rechargeable nonaqueous electrolytic battery, it comprises positive pole, negative pole and the nonaqueous electrolyte between described positive pole and described negative pole, wherein,
Described positive pole comprises the anode mixture layer;
Described negative pole comprise contain can embed, the anode mixture layer of the active material of removal lithium embedded ion and support the collector body of described anode mixture layer; And the surface of described anode mixture layer with the opposed place of described anode mixture layer a plurality of mixture layer expansion absorption ditches are set, described collector body is exposed.
2, rechargeable nonaqueous electrolytic battery according to claim 1, wherein, described anode mixture layer is divided into independently a plurality of intervals by described mixture layer expansion absorption ditch.
3, rechargeable nonaqueous electrolytic battery according to claim 1, wherein, described positive pole and described negative pole are reeled; Interior all sides when described mixture layer expansion absorption ditch is set at the coiling of the described at least collector body in the described anode mixture layer.
4, rechargeable nonaqueous electrolytic battery according to claim 3, wherein, the coiling direction of described mixture layer expansion absorption ditch and described negative pole comes down to vertically disposed.
5, rechargeable nonaqueous electrolytic battery according to claim 3, wherein, the end of the outer surface of adjacent described anode mixture layer is mutual butt by described mixture layer expansion absorption ditch.
6, rechargeable nonaqueous electrolytic battery according to claim 1, wherein, the volume of described active material under charged state is more than 1.2 with respect to the ratio of the volume under discharge condition.
7, rechargeable nonaqueous electrolytic battery according to claim 6, wherein, described anode mixture layer further comprises: be attached to the surface of described active material carbon nano-fiber, be used to promote at least a kind of catalyst elements that is selected from Cu, Fe, Co, Ni, Mo and Mn first of the growth of described carbon nano-fiber;
Described active material and described carbon nano-fiber and described catalyst elements have formed composite negative electrode active material.
8, rechargeable nonaqueous electrolytic battery according to claim 1, wherein, described active material is a material.
9, rechargeable nonaqueous electrolytic battery according to claim 8, wherein, described material is by SiO
xThe silica of expression, 0.05<x in the formula<1.95.
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CN101165948B (en) * | 2005-10-17 | 2011-04-20 | 三星Sdi株式会社 | Anode active material, method of preparing the same, and anode and lithium battery containing the material |
CN102820451A (en) * | 2012-07-23 | 2012-12-12 | 深圳市海太阳实业有限公司 | Negative electrode pole piece and preparation method thereof, and lithium ion battery and preparation method thereof |
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CN101165948B (en) * | 2005-10-17 | 2011-04-20 | 三星Sdi株式会社 | Anode active material, method of preparing the same, and anode and lithium battery containing the material |
US8628884B2 (en) | 2005-10-17 | 2014-01-14 | Samsung Sdi Co., Ltd. | Anode active material, method of preparing the same, and anode and lithium battery containing the material |
CN103367793A (en) * | 2012-03-27 | 2013-10-23 | Tdk株式会社 | Lithium-ion secondary battery |
CN103367793B (en) * | 2012-03-27 | 2016-04-06 | Tdk株式会社 | Lithium rechargeable battery |
CN102820451A (en) * | 2012-07-23 | 2012-12-12 | 深圳市海太阳实业有限公司 | Negative electrode pole piece and preparation method thereof, and lithium ion battery and preparation method thereof |
CN105051949A (en) * | 2013-03-26 | 2015-11-11 | 三洋电机株式会社 | Negative electrode for non-aqueous electrolyte secondary batteries and non-aqueous electrolyte secondary battery |
CN105074969A (en) * | 2013-03-26 | 2015-11-18 | 三洋电机株式会社 | Negative electrode for non-aqueous electrolyte secondary batteries and non-aqueous electrolyte secondary battery |
TWI622209B (en) * | 2013-05-31 | 2018-04-21 | Yasunaga Kk | Electrode for nonaqueous electrolyte secondary battery and method for producing nonaqueous electrolyte secondary battery |
CN107978762A (en) * | 2016-10-21 | 2018-05-01 | 罗伯特·博世有限公司 | Electrode with the conductive grid in active material structure |
CN113937248A (en) * | 2020-07-14 | 2022-01-14 | 中国科学院宁波材料技术与工程研究所 | Preparation method of material capable of removing/embedding alkali metal ions |
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