CN101740811B - Secondary cell and anode - Google Patents

Abstract

Provide and be obtained in that excellent cycle characteristics and the secondary cell of excellent expansion characteristics.This secondary cell includes negative electrode and the anode that can embed and deviate from electrode reaction thing；And containing solvent and the electrolyte of electrolytic salt.Anode has anode active material layers in anode collector.This anode active material layers comprises and multiple has the silicon (Si) the crystalline state anode active material particles as constituent element.The plurality of anode active material particles comprises spheroidal particle and aspherical particle.

Description

Secondary cell and anode

Background technology

1. invention field

The present invention relates to that there is in anode collector the anode active material layers that can embed and deviate from electrode reaction thing Anode and use the secondary cell of this anode.

2. description of Related Art

In recent years, be widely used portable electron device such as video camera, digital still camera, mobile phone and Notebook-PC, needs reduce their size and weight and realize their long-life strongly.Accordingly, as The power supply of portable electron device, has been developed for battery, is particularly provided that the little of high-energy-density and lightweight secondary Battery.

Especially, the lithium rechargeable battery utilizing the embedding of lithium ion and taking off to carry out discharge and recharge reaction obtains extensively Actual application, this is because such lithium rechargeable battery is provided that energy more higher than lead battery and nickel-cadmium cell is close Degree.

Lithium rechargeable battery includes that negative electrode, anode and electrolyte, described negative electrode contain and can embed and deviate from lithium ion Active material of cathode, described anode contains the active material of positive electrode that can embed and deviate from lithium ion.

As active material of positive electrode, material with carbon element is used widely.But, in recent years, along with having developed portable electronic The high-performance of device and multi-functional, needs to improve further battery capacity.Accordingly, it is considered to use silicon to replace material with carbon element.Because silicon Theoretical capacity (4199mAh/g) be significantly higher than the theoretical capacity (372mAh/g) of graphite, thus be expected to highly improve battery and hold Amount.

Use silicon as in the situation of active material of positive electrode, use vapour deposition process such as evaporation as forming anode The method of active material layer.In this case, silicon is deposited directly on the surface of anode collector, and active material of positive electrode is even Receiving in (being fixed on) anode collector, therefore when charging and discharging, anode active material layers expands hardly and shrinks.

But, in this case, the misgivings existed are owing to following reason reduces as the important spy of secondary cell Property cycle characteristics and expand (swollenness) characteristic.

First, when charging and discharging, the active material of positive electrode embedding lithium ion becomes high activity.Therefore, electrolyte Easily decomposes, and part lithium ion is prone to become inertia.Therefore, after recharge and electric discharge, due to the decomposition of electrolyte, Discharge capacity is prone to reduce and be prone in the battery to produce gas.

Second, even if active material of positive electrode is connected to anode collector, depend on the anode activity when charging and discharging , there is the probability that anode active material layers is destroyed and comes off from anode collector in the expansion of material layer and shrinkage degree. Thus, after recharge and electric discharge, discharge capacity is prone to reduce.If it addition, anode active material layers expand consumingly and Shrinking, result anode collector becomes to be easily deformed.

3rd, because siliceous deposits film becomes amorphous state (amorphous), active material of positive electrode is susceptible to the impact of oxidation.Cause This, the physical property of active material of positive electrode deteriorated with the working time, and anode active material layers and anode collector Contact strength is prone to reduce.Therefore, after recharge and electric discharge, discharge capacity is prone to reduce.

Therefore, for improving the cycle characteristics etc. of lithium rechargeable battery, it is proposed that some technology.Especially, anode is lived Property material be formed as comprising crystalline domain and amorphous areas (such as, with reference to WO.01/029912).It addition, use multiple comprising Silicon and the anode active material particles of lithium and be incorporated into (such as, with reference to Japanese Unexamined Patent by being sintered or melt The open No.2006-269331 of application).It addition, formation anode active material layers so that have by using vapour deposition process raw The lower floor of long primary particle is stacking (such as, reference with the upper strata of the second particle having by using cladding process deposition Japanese Unexamined Patent Application Publication No.2007-122915).

Summary of the invention

In recent years, along with the high-performance of portable electron device with multi-functional day by day develop, its power consumption tends to increasing. Therefore, it is intended to frequently repeat the charging and discharging of secondary cell.Therefore, in order to frequently and safely use secondary cell, Crave for and improve cycle characteristics and expansion characteristics further.

In view of the foregoing, in the present invention, it is desirable to provide be obtained in that the cycle characteristics of excellence and excellent expansion are special The anode of property and use the secondary cell of this anode.

According to embodiment of the present invention, it is provided that the negative electrode that includes embedding and to deviate from electrode reaction thing and anode with And the secondary cell of electrolyte, described electrolyte contains solvent and electrolytic salt.Anode has anode in anode collector and lives Property material layer.Anode active material layers comprises and multiple has the silicon crystalline state anode active material particles as constituent element (element). The plurality of anode active material particles comprises spheroidal particle and aspherical particle.According to embodiment of the present invention, it is provided that Can embed and deviate from electrode reaction thing and there is in anode collector the anode of anode active material layers.Anode activity material The bed of material comprises and multiple has the silicon crystalline state anode active material particles as constituent element, and the plurality of anode active material particles Comprise spheroidal particle and aspherical particle.

Anode according to embodiments of the present invention, anode active material layers comprise multiple have silicon as constituent element crystalline state sun Pole active material particle, and the plurality of anode active material particles comprises spheroidal particle and aspherical particle.Thus, anode The physical property of active material particle deteriorated little with the working time.It addition, when electrode reaction, anode active material layers Expand hardly and shrink, and therefore anode collector deforms hardly.Therefore, according to the anode using embodiment of the present invention Secondary cell, it is possible to obtain excellent cycle characteristics and excellent expansion characteristics.

Other of the present invention substantially more will be presented by described below with other objects, features and advantages.

Accompanying drawing explanation

Fig. 1 is the cross sectional view showing anode construction according to embodiments of the present invention；

Fig. 2 A and Fig. 2 B is SEM photograph and the schematic diagram thereof of the cross section structure showing anode shown in Fig. 1；

Fig. 3 A and Fig. 3 B is SEM photograph and the schematic diagram thereof of another cross section structure showing anode shown in Fig. 1；

Fig. 4 is the SEM photograph of the surface texture showing anode shown in Fig. 1；

Fig. 5 A and Fig. 5 B is SEM photograph and the schematic diagram thereof of the another cross section structure showing anode shown in Fig. 1；

Fig. 6 A and Fig. 6 B is SEM photograph and the schematic diagram thereof of the another cross section structure showing anode shown in Fig. 1；

Fig. 7 is to show that the cross section including the structure of the first secondary cell of anode according to embodiments of the present invention regards Figure；

Fig. 8 is the cross sectional view taken along the line VIII-VIII of the first secondary cell shown in Fig. 7；

Fig. 9 is the plan view of the structure showing negative electrode shown in Fig. 8 and anode；

Figure 10 is that the cross section of the structure of the second secondary cell showing and including anode according to embodiments of the present invention regards Figure；

Figure 11 is the cross sectional view of the amplifier section showing spiral winding electrode shown in Figure 10；

Figure 12 is to show to include that the decomposition of the structure of the third secondary cell of anode according to embodiments of the present invention is saturating View；

Figure 13 is the cross sectional view taken along the line XIII-XIII of screw winding body shown in Figure 12；

Figure 14 is the coordinate diagram showing the relation between particle diameter and discharge capacitance/expansion rate；

Figure 15 is the coordinate diagram showing the relation between circularity and discharge capacitance/expansion rate；

Figure 16 is the coordinate diagram showing the relation between numbers of particles and discharge capacitance/expansion rate；

Figure 17 is the coordinate diagram showing the relation between half-peak breadth and discharge capacitance/expansion rate；

Figure 18 is the coordinate diagram showing the relation between oxygen content and discharge capacitance/expansion rate；With

Figure 19 is the coordinate diagram of the relation between number and the discharge capacitance/expansion rate showing high oxygen-containing region；

Figure 20 is 10 mean roughness (ten point height of roughnessprofile) Rz of display and puts The coordinate diagram of the relation between capacitance conservation rate/expansion rate；

Detailed description of the invention

Embodiment of the present invention are described in detail hereinafter with reference to accompanying drawing.Description will be provided by following order.

1. anode

2. use the electrochemical appliance (secondary cell) of anode

The first secondary cell of 2-1. (square)

2-2. the second secondary cell (column type)

The third secondary cell of 2-3. (lamination membranous type)

1. anode

Fig. 1 shows the cross section structure of anode according to embodiments of the present invention.This anode such as fills for electrochemistry Put such as secondary cell.This anode has anode collector 1 and provides the anode active material layers 2 in this anode collector 1, institute State anode collector 1 and there is an opposite.

Anode collector

Anode collector 1 is preferably by having favourable electrochemical stability, favourable electric conductivity and favourable mechanical strength Material make.The example of such material includes copper, nickel and rustless steel.Especially, copper is preferred, this is because thus obtain Obtain high electric conductivity.

The surface of anode collector 1 is the most roughened.Thus, due to so-called Anchoring Effect (anchor effect), The contact performance between anode collector 1 and anode active material layers 2 can be improved.In this case, will at least with sun The rough surface of the anode collector 1 in the region that pole active material layer 2 is relative is enough.The example bag of roughening method Include and form fine grain method by electrolysis process.Electrolysis process be by a cell by electrolysis in anode collector 1 Surface on form fine grained and depression and protruding method be provided.By the Copper Foil commonly referred to " electricity using electrolysis to be formed Solve Copper Foil ".The method that the example of other roughening method includes the Copper Foil of rolling is carried out sandblasting.

10 mean roughness Rz on the surface of anode collector 1 are not particularly limited, but particularly preferably 1.5 μm or more Greatly.In this case, 10 mean roughness Rz are more preferably 1.5 μm-30 μm (including two end values), more preferably 3 μm-30 μm (includes two end values), contacts spy because improving the most further between anode collector 1 with anode active material layers 2 Property.More particularly, if less than 1.5 μm, there is the probability that can not obtain sufficient contact performance.Meanwhile, if greatly In 30 μm, there is the probability reducing contact performance.

Anode active material layers

Anode active material layers 2 such as provides on two surfaces of anode collector 1.But, anode active material layers 2 Can be provided in only on the single surface of anode collector 1.

Anode active material layers 2 can embed and deviate from the anode of electrode reaction thing such as lithium ion containing one or more Material is as active material of positive electrode.If necessary, anode active material layers 2 can comprise it together with aforesaid anode active material Its material such as conductive agent.

As anode material, having silicon is preferably as such material has embedding and de-as the material of constituent element Go out the excellent ability of electrode reaction thing and therefore, it is possible to provide high-energy-density.The example of such material include silicon simple substance, Alloy or compound, or at least partly there is the material of one or more phase.In particular it is preferred to the simple substance of silicon, alloy and At least one in compound, more preferably elementary silicon.

" alloy " in the present invention, in addition to the alloy with two or more metallic elements, also includes having one Or the alloy of Determination of multiple metal elements and one or more metalloid elements.Self-evident, aforementioned " alloy " in the present invention can To have nonmetalloid.Its structure include solid solution, eutectic crystal (eutectic mixture), intermetallic compound and Wherein two or more structures coexisted in them.

The example of silicon alloy include having in addition to silicon at least one in following elements as the alloy of constituent element.That is, described The example of element includes stannum, nickel, copper, ferrum, cobalt, manganese, zinc, indium (In), silver, titanium, germanium, bismuth (Bi), antimony and chromium.

The example of silicon compound includes the compound having oxygen and carbon (C) in addition to silicon as constituent element.Silicon compound can be with example As having in addition to silicon, one or more in the aforementioned elements of constituent element are described as with regard to silicon alloy.

The alloy of silicon or the example of compound include as follows.That is, its example includes SiB₄、SiB₆、Mg₂Si、Ni₂Si、 TiSi₂、MoSi₂、CoSi₂、NiSi₂、CaSi₂、CrSi₂、Cu₅Si、FeSi₂、MnSi₂、NbSi₂And TaSi₂.It addition, its example bag Include VSi₂、WSi₂、ZnSi₂、SiC、Si₃N₄、Si₂N₂O、SiO_v(0 ＜ v≤2), SnO_w(0 ＜ w≤2) and LiSiO.

In addition to aforementioned silicon, active material of positive electrode the most also has oxygen as constituent element, this is because thereby inhibiting electrode The expansion of anode active material layers 2 and contraction during reaction.In this case, at least part of oxygen is preferably combined with part silicon.Knot Conjunction state can be the form of silicon monoxide, silicon dioxide, or the form of other metastable state.

Oxygen content in active material of positive electrode is not particularly limited, but preferably 1.5 atom %-40 atom % (include two Individual end value), this is because the most more prevent expansion and the contraction of anode active material layers 2.More particularly, it is less than when oxygen content During 1.5 atom %, the probability of Shortcomings expansion and contraction to prevent anode active material layers 2.Meanwhile, big when oxygen content When 40 atom %, then can exceedingly improve resistance.It is used for together with electrolyte in the situation of electrochemical appliance at anode, anode Active material does not include the coating being decomposed to form by electrolyte etc..That is, when the oxygen content calculated in active material of positive electrode, Oxygen in above-mentioned coating does not counts.

The active material of positive electrode with oxygen is by such as introducing oxygen into shape in room continuously when deposition anode material Become.Especially, if only there is no required oxygen content by introducing oxygen, it is also possible to introduce liquid (such as in room Steam etc.) as the supply source of oxygen.

It addition, in addition to aforementioned silicon, active material of positive electrode the most also has metallic element as constituent element, this is because thus Reduce the resistance of active material of positive electrode, and more suppression electrode reaction time the expansion of anode active material layers 2 and contraction.This The example of the metallic element of sample includes at least one in following elements.That is, its example include ferrum, nickel, molybdenum, titanium, chromium, cobalt, copper, Manganese, zinc, germanium, aluminum, zirconium, silver, stannum, antimony and tungsten.Metal element content in active material of positive electrode is not particularly limited.But, Anode is in the situation of secondary cell, if this metal element content is excessive, should improve the thickness of anode active material layers 2 with Battery capacity needed for acquisition, therefore can destroy anode active material layers 2, and anode active material layers 2 can be from anode current collector Body 1 peels off.

Active material of positive electrode can all have metallic element, or can partly have metallic element.In this situation In, the state of active material of positive electrode can be complete alloyed state (alloyed state), or not exclusively alloying state and It it is the state (compound state or phase-separated state) that wherein silicon mixes mutually with metallic element.The state of active material of positive electrode can be led to Cross such as energy-dispersion X-ray fluorescence spectrometry (EDX) to check.

Such as, by using alloying pellet as forming material or by metal material and anode in deposition anode material Material deposits together, forms the active material of positive electrode with metallic element.

It addition, anode active material layers 2 preferably includes (at thickness direction) in layer that the height with higher oxygen content is oxygen-containing Region and there is the low oxygen-containing region compared with low oxygen content, this is because prevent the swollen of anode active material layers 2 when electrode reaction Swollen and shrink.Oxygen content in low oxygen content region is the least.Oxygen content in elevated oxygen level region is such as similar to Oxygen content in above-mentioned active material of positive electrode.

In this situation, the highest oxygen-containing region is clipped between low oxygen-containing region, and the most oxygen-containing region and height contain Oxygen region replaces and repeatedly stacking, this is because the most more prevent expansion and the contraction of anode active material layers 2.Contain low In the alternately laminated situation in oxygen region and the oxygen-containing region of height, elevated oxygen level region and low oxygen content region alternately and are repeatedly distributed In anode active material layers 2.

By such as introducing oxygen into when deposition anode material in room intermittently or changing the oxygen introduced in room Amount is formed containing high oxygen-containing region and the anode active material layers in low oxygen-containing region.Self-evident, only by introducing oxygen Can not obtain in the situation of requisite oxygen content, it is also possible in room, introduce liquid (such as steam etc.).

It is possible that the oxygen content in high oxygen-containing region differs markedly from the oxygen content in low oxygen-containing region, or high oxygen-containing district The oxygen content in territory is not sufficiently different from the oxygen content in low oxygen-containing region.Especially, become continuously in aforementioned oxygen introduction volume In the situation changed, oxygen content can change continuously.In the situation that oxygen introduction volume changes off and on, high oxygen-containing region and low Oxygen-containing region becomes so-called " layer ".Meanwhile, in the situation that the introduction volume of oxygen changes continuously, high oxygen-containing region and low contain Oxygen region becomes " lamellar (1amellar state) " rather than " layer ".In the later case, preferably oxygen content is oxygen-containing at height Change incrementally or continuously between region and low oxygen-containing region.If oxygen content changes tempestuously, then exist and reduce ion Diffusion property or make the probability that resistance increases.

It addition, active material of positive electrode is crystalline state, and it is little affected by the impact of oxidation.Therefore, the thing of active material of positive electrode Rationality can deteriorate little with the working time, and the contact performance of anode active material layers 2 and anode collector 1 is hardly Reduce.

The crystal state (crystalline state or amorphous state) of active material of positive electrode can be checked by X-ray diffraction.Especially, as Really the analysis result of active material of positive electrode detects sharp peak, then this active material of positive electrode is crystalline state.Meanwhile, if anode is active The analysis result of material detects broad peak, then this active material of positive electrode is amorphous state.

Diffraction maximum half-peak breadth (2 θ) in (111) crystal face of the active material of positive electrode obtained by X-ray diffraction is by spy Definite limitation, but preferably 20 degree or less.It addition, the crystallite dimension coming from this crystal face is not particularly limited, it is particularly preferred, however, that 10nm or bigger.Thus, the physical property of active material of positive electrode deteriorated little with the working time, and electrode reaction thing Diffusion property reduces hardly.

Active material of positive electrode is preferably attached to the surface of anode collector 1.Thus, anode active material layers 2 physics is fixed In anode collector 1, and therefore anode active material layers 2 expands hardly when electrode reaction and shrinks.Aforementioned wording " sun Pole active material is connected to the surface of anode collector 1 " represent that anode material is deposited directly on the surface of anode collector 1. Therefore, in the situation being formed anode active material layers 2 by painting method, sintering method etc., active material of positive electrode is the most straight Receive the surface of anode collector 1 in succession.In this case, active material of positive electrode is connected indirectly to anode collector 1, other Between material (such as binding agent etc.) is in, or active material of positive electrode is only neighbouring with the surface of anode collector 1.

It is enough that active material of positive electrode is at least partly connected to the surface of anode collector 1 with it.If its at least portion Divide and be connected to anode collector 1, be not connected to the situation on the surface of anode collector 1 compared to active material of positive electrode, change It is apt to the contact strength of anode active material layers 2 and anode collector 1.Connect with anode collector 1 at segment anode active material In the situation touched, anode active material layers 2 has part that wherein active material of positive electrode contacts and wherein with anode collector 1 The part that active material of positive electrode does not contacts with anode collector 1.

Not there is the situation of the wherein part that active material of positive electrode does not contacts with anode collector 1 at active material of positive electrode In, whole active material of positive electrode contact with anode collector 1, the electronic conductivity between therefore improve.Meanwhile, in this feelings In shape, the outlet (slack space) that during electrode reaction, anode active material layers 2 expands and shrinks in situation does not exists.Therefore, it is subject to During consequent stress influence, anode collector 1 deformable.

Meanwhile, there are the feelings of the wherein part that active material of positive electrode does not contacts with anode collector 1 at active material of positive electrode In shape, the outlet (slack space) that during electrode reaction, anode active material layers 2 expands and shrinks in situation exists.Therefore, by answering The deformation of the anode collector 1 of power impact occurs hardly.Meanwhile, because exist in which active material of positive electrode not with anode current collector The part of body 1 contact, the electronic conductivity between therefore can reducing.

In this case, active material of positive electrode 2 preferably has space.Thus, it is thus achieved that when electrode reaction, anode is lived Property material layer 2 expands and shrinks the outlet (slack space) in situation, and therefore anode active material layers 2 expands hardly and receives Contracting.

It addition, active material of positive electrode preferably carries out alloying with anode collector 1 in their at least part of interface.Cause And, improve the contact strength of anode active material layers 2 and anode collector 1, and the therefore anode activity material when electrode reaction The bed of material 2 expands hardly and shrinks.It addition, the electronics conduction thus improved between anode collector 1 and anode active material layers 2 Property." alloying " had both included that the constituent element of anode collector 1 and the constituent element of active material of positive electrode formed the situation of complete alloying, again Situation including the mixing of the two constituent element.In later case, in its interface, the constituent element of anode collector 1 can be at sun Spreading in the active material of pole, the constituent element of active material of positive electrode can spread in anode collector 1, or these constituent elements can be Spread one another.

Especially, active material of positive electrode is the state of multiple granule.In this case, active material of positive electrode can have The single layer structure that formed by single deposition step or can have the multiple structure formed by multiple deposition steps.So And, if deposition step is relevant with high heat, then active material of positive electrode preferably has multiple structure.It is divided into some steps at deposition step Situation in, anode collector 1 open-assembly time at high heat is shorter than the situation carrying out depositing in single deposition step.

The plurality of particulate anodes active material (anode active material particles) contains spheroidal particle and aspherical particle. In this case, do not comprise the situation of spheroidal particle compared to anode active material particles, the anode activity when electrode reaction Material layer 2 expands hardly and shrinks, and therefore anode collector 1 deforms hardly.More particularly, spheroidal particle due to its with The high resistance that aspherical particle is compared, contributes to electrode reaction more hardly, and therefore spheroidal particle is several when electrode reaction Do not expand and shrink.Thus, even if aspherical particle expands and shrinks and therefore produce internal stress when electrode reaction, but should Internal stress is relaxed by spheroidal particle, and correspondingly anode collector 1 deforms because of the impact of internal stress hardly.

Aforementioned " spheroidal particle " is such granule, i.e. by using scanning electron microscope (SEM) with 8000 times put When big multiplying power observes the surface of anode active material layers 2, it is possible to be recognized as the granule with spheric profile.Meanwhile, " aspherical Grain " it is the granule in addition to aforementioned spheroidal particle, and the most such granule, i.e. by using SEM (enlargement ratio: 8000 When observing again) surface of anode active material layers 2, it is possible to be recognized as the granule with polygon or sheet profiles.

The number of spheroidal particle is not particularly limited.If comprising at least one spheroidal particle, spherical compared to not containing The situation of granule, anode collector 1 becomes to deform hardly.But, if being helpless to the number of the spheroidal particle of electrode reaction Excessive, then can reduce embedding and the abjection amount of electrode reaction thing.More particularly, if this anode is for secondary cell, then battery Capacity can reduce.Therefore, the number of spheroidal particle is preferably 10pcs-200pcs (including two end values).

By using the image on 30 anode active material layers 2 surfaces of SEM (enlargement ratio: 8000 times) shooting, (SEM schemes Picture), count the spheroidal particle number of each image, and then the count number of each image is averaged, it is thus achieved that above-mentioned ball Shape numbers of particles.In this case, the observation scope (term of reference) carried out by SEM is 10.75 μm height and 16.00 μm Wide.It addition, be not counted in the granule (partial contour is at the separate granule in the edge of image) that its profile is not included in an image.

In the number of counting spheroidal particle, the most only count spherical in given range of particle diameter (median size) Grain.Thus, it is therefore prevented that by whether counting the artificial change that molecule causes, and prevent and count huge exotic mistakenly Matter such as dust.Aforementioned given range for example, 0.1 μm-40 μm (includes two end values).Self-evident, some spheroidal particle have There is the particle diameter less than 0.1 μm.Compared to particle diameter spheroidal particle within the above range, the most small spheroidal particle tends to several Do not make the internal stress relaxation produced in anode active material layers 2.Therefore, in for making practically in anode active material layers 2 Stress relaxation, it is enough that attention concentrates merely on particle diameter spheroidal particle within the above range.

The particle diameter (median size) of spheroidal particle is more preferably 0.5 μm-35 μm (including two end values), this is because anode Active material layer 2 thus expands more hardly when electrode reaction and shrinks, and the embedding of electrode reaction thing and abjection amount Reduce hardly.More particularly, if the particle diameter of spheroidal particle (median size) is less than 0.5 μm, then spheroidal particle can be hardly Make the internal stress relaxation in anode active material layers 2.Meanwhile, if the particle diameter of spheroidal particle (median size) is more than 35 μm, can Reduce embedding and the abjection amount of electrode reaction thing.In this case, if this anode is for secondary cell, then battery can be reduced Capacity.The computational methods of above-mentioned spheroidal particle particle diameter are similar to the computational methods with regard to the situation described by spheroidal particle number.

The circularity of spheroidal particle is not particularly limited.But, if circularity is too low, then spheroidal particle makes sun hardly The internal stress relaxation produced in pole active material layer 2.Therefore, circularity is preferably 0.5-1 (including two end values).Above-mentioned spherical The computational methods of particle circularity are similar to the computational methods with regard to the situation described by spheroidal particle number.By by spheroidal particle Girth calculate circularity divided by the girth of the circle corresponding to this spheroidal particle area.

The shape of spheroidal particle can be any shape, but especially, at least part of spheroidal particle is preferably flat.Cause And, it is easy to make each active material of positive electrode contact with each other and be prone to be laminated to each other, therefore increasing each anode active material particles Between the number of contact point.Thus, improve the electronic conductivity in anode active material layers 2.Aforementioned " flat " represents spherical Granule is in the shape extended along anode collector 1 surface direction, is i.e. the shape of approximate ellipsoidal, and this shape has along sun Major axis on the direction on pole collector 1 surface and have with the short axle on the direction of its surface traversed by.Such pancake Shape for example is by the characteristic shown in the situation of spraying process deposition anode material.In this case, if improving anode material The fusion temperature of material, then anode active material particles tends in flat.

It is possible that spheroidal particle and aspherical particle are evenly distributed or are distributed unevenly.It addition, spheroidal particle With the position relationship (vertical relation etc.) between aspherical particle is not particularly limited.As long as anode active material layers 2 is wrapped in the lump Containing spheroidal particle and aspherical particle, then anode collector 1 deforms hardly.

Anode active material layers 2 is formed by such as spraying process.In this case, by by molten state or semi-molten The anode material of state forms anode active material layers towards anode collector 1 injection.Thus, as it has been described above, in anode activity In material layer 2, active material of positive electrode is crystalline state, and is connected to the surface of anode collector 1.

Anode active material layers 2 can comprise other anode material, as long as anode active material layers 2 is containing having silicon conduct The material of constituent element is as anode material.

The example of other anode material includes to embed and deviating from electrode reaction thing and have metallic element and quasi-gold Belong at least one in element as constituent element material (except have silicon as the material of constituent element in addition to) because such material carries For high-energy-density.This material can be metallic element or the simple substance of metalloid element, alloy or compound, or can be at least Part has their one or more phases.

The example of aforesaid metal elements or aforementioned metalloid element includes can be with the metal of electrode reaction thing formation alloy Element or metalloid element.Its object lesson is at least one in lower surface element.That is, its example include magnesium, boron, aluminum, gallium, Indium, germanium, stannum and lead (Pb).Additionally, its example includes bismuth, cadmium (Cd), silver, zinc, hafnium (Hf), zirconium, yttrium (Y), palladium (Pd) and platinum (Pt).In particular it is preferred to stannum.Stannum has embedding and deviates from the ability of electrode reaction thing, is thus provided that high-energy-density.Tool The example having the material of stannum includes the simple substance of stannum, alloy or compound, and at least partly has their one or more phases Material.

The example of ashbury metal include having at least one in lower surface element as the alloy of the constituent element in addition to stannum: silicon, nickel, Copper, ferrum, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony and chromium.The example of tin compound includes containing aerobic or carbon in addition to stannum as group The compound of unit.Tin compound can have one or more with regard to the element described by ashbury metal as the constituent element in addition to stannum.Stannum Alloy or the example of compound include SnSiO₃, LiSnO and Mg₂Sn。

Particularly as having the material of stannum, for example, it is preferable to also have in addition to the stannum as the first constituent element the second constituent element and The material of third element, because thus improve cycle characteristics at anode in the situation of secondary cell.Under second constituent element is At least one in surface element.That is, its example includes cobalt, ferrum, magnesium, titanium, vanadium, chromium, manganese, nickel, copper, zinc, gallium and zirconium.Its other example Attached bag includes niobium, molybdenum, silver, indium, cerium (Ce), hafnium, tantalum, tungsten, bismuth and silicon.Third element is at least one in boron, carbon, aluminum and phosphorus.

In particular it is preferred to have stannum, cobalt and carbon containing SnCoC material, in this material, carbon content is 9.9 weight %-29.7 Weight % (includes two end values), and (Co/ (Sn+Co)) content of stannum and cobalt (includes two than preferably 20 weight %-70 weight % Individual end value).In such compositing range, it is possible to obtain high-energy-density.Containing in SnCoC material, preferably at least part is made Carbon for constituent element is combined with metallic element or the metalloid element as other constituent element.Thus prevent cohesion or the crystallization of stannum etc. Change.

The material containing SnCoC has the phase comprising stannum, cobalt and carbon.Such phase is preferably low crystallization phase or Amorphous Phase.Should Being the reaction phase can reacted with electrode reaction thing mutually, such reaction contributes to obtaining excellent characteristic mutually.Use wherein CuK alpha ray, as in specific X-ray and situation that sweep rate is 1 degree/min, spends (including two end values) at 20 degree-50 The angle of diffraction 2 θ in, the half-peak breadth of the diffraction maximum obtained by the X-ray diffraction of this phase is preferably 1 degree or bigger.Thus, more flat Embed and deviate from electrode reaction thing quietly, and reduce and the reactivity of electrolyte etc..In some cases, except low crystallization mutually or Outside Amorphous Phase, containing SnCoC material, also there is the simple substance comprising every kind of element or part thereof of phase.

Other element can be comprised the most further containing SnCoC material.As other element, preferably silicon, ferrum, nickel, Chromium, indium, niobium, germanium, titanium, molybdenum, aluminum, phosphorus, gallium or bismuth etc..Two or more in them can be had containing SnCoC material.

In addition to containing SnCoC material, further preferably have stannum, cobalt, ferrum and carbon containing SnCoFeC material.Can arbitrarily set Composition containing SnCoFeC material.Such as, wherein iron content is set as that little composition is as follows.That is, carbon content is 9.9 weight %- 29.7 weight % (include two end values), and iron content is 0.3 weight %-5.9 weight % (including two end values), and stannum and cobalt (Co/ (Sn+Co)) content ratio be 30 weight %-70 weight % (including two end values).It addition, such as, wherein iron content sets The composition determining greatly is as follows.That is, carbon content is 11.9 weight %-29.7 weight % (including two end values), stannum, cobalt and ferrum ((Co+Fe)/(Sn+Co+Fe)) content ratio is 26.4 weight %-48.5 weight % (including two end values), cobalt and the (Co/ of ferrum (Co+Fe)) content ratio is 9.9 weight %-79.5 weight % (including two end values).In such compositing range, it is thus achieved that High-energy-density.Physical property etc. containing SnCoFeC material is similar to those containing SnCoC material aforementioned.

The example of other anode material includes material with carbon element.In material with carbon element, embedding with electrode reaction thing and deviate from relevant Changes in crystal structure the least, thereby is achieved high-energy-density.It addition, material with carbon element acts also as conductive agent.The example of material with carbon element Son can include the non-graphitized carbon that spacing is 0.37nm or bigger in graphitized carbon, wherein (002) face, wherein (002) face Spacing is the graphite etc. of 0.34nm or less.More particularly, its example includes pyrolytic carbon, coke, vitreous carbon fiber, You Jiju Compound roasting body, activated carbon and white carbon black.In above-mentioned, coke includes pitch coke, needle coke and petroleum coke.Organic polymer Thing roasting body is obtained by roasting at a proper temperature and carbonized phenolic resin, furane resins etc..The shape of material with carbon element can Being fibrous, spherical, granular and any shape in flakey.

It addition, the example of other anode material includes metal-oxide and polymer.Metal-oxide be such as ferrum oxide, Ruthenium-oxide, molybdenum oxide etc..Polymer is such as polyacetylene, polyaniline, polypyrrole etc..

Self-evident, anode material can be the material beyond above-mentioned material.Furthermore it is possible to by being arbitrarily used in mixed way two Plant or more kinds of above-mentioned anode material.

Anode active material layers 2 preferably at least part of gap location between anode active material particles has metal level. Thus, because the metal level between anode active material particles utilizes is bonded to each other, even if anode active material layers 2 is anti-at electrode Seasonable expansion and contraction, anode active material layers 2 is not destroyed or comes off from anode collector 1.Especially, if anode material Material is to have interatomic bond to make a concerted effort the weak silicon material as constituent element, the most effectively prevents coming off of anode active material layers 2.Separately Outward, because metal level plays the effect of protecting film, it is therefore prevented that with during electrode reaction activation anode active material particles contact and The decomposition reaction caused.The example of material that its decomposition reaction obtains preventing includes being used together with anode in the secondary battery Electrode.

As it has been described above, it is enough for providing metal level at least part of gap.If provided at least part of gap Metal level, then obtain the foregoing advantages different from the situation not providing metal level.Self-evident, metal level is in gap Occupation rate is the biggest, this is because improve foregoing advantages the most further.

In this case, metal level preferably covers at least part of surface of anode active material particles.Thus, anode is lived Property material granule be prone to between metal level be combined, and this metal level is prone to play the work of protecting film in relative broad range With.Therefore, the coverage of metal level is the widest, this is because be derived from higher effect.Especially, if position The surface of the anode active material particles in the uppermost surface layer of anode active material layers 2 is coated with metal level, then electrolyte Deng decomposition reaction effectively prevented.

Metal level preferably comprises the material not making metal level and electrode reaction thing react as constituent element, in order to prevent at electrode Embedding and the abjection of electrode reaction thing is suppressed during reaction.Especially, such metal level preferably comprise ferrum, cobalt, nickel, zinc, copper and At least one in chromium, because such element reacts with various electrode reaction thing such as lithium ions hardly, and demonstrates Excellent combined function and defencive function.But, the material constituting metal level is not limited to metal simple-substance, and can be alloy, gold Belong to compound or comprise the mixture of two or more in them.Self-evident, metal level can be containing except aforementioned ferrum Metallic element outside Deng.

The thickness of metal level is not particularly limited, but in particular it is preferred to be 1nm-30000nm (including two end values), because of For being derived from higher effect.More particularly, if thickness is less than 1nm, then metal level amount is too small, therefore exists and there is no Enough combined function and the probability of enough defencive functions.Meanwhile, if thickness is more than 30000nm, metal level amount is excessive, The embedding of electrode reaction thing and deviate from probability hindered when there is electrode reaction.To describe (with reference to Fig. 6 A and 6B) after a while The definition (calculation procedure) of metal layer thickness.

The forming method of metal level is not particularly limited, but in particular it is preferred to electrolytic plating method or electroless plating method, and And electrolytic plating method and electroless plating method can be used together, this is because thus plating film is prone to growth hence into anode In gap between active material particle, and cover the surface of anode active material particles.

The formation process of the anode active material layers 2 comprising metal level is not particularly limited, as long as finally in anode activity Gap between material granule is formed metal level.

For example, it is possible to, by using electroless plating method, electrolytic plating method etc. to be initially formed metal level to cover Behind the surface of the anode material being made up of multiple granules, by spraying process deposition anode material.In this case, when anode material When expecting to spray with molten state or semi-molten state, spray the metal level of similar state together with this.Therefore, at anode activity material Gap between material granule forms metal level.Such as in the situation that the ideal thickness ground of metal level is relatively large, such shape One-tenth method is effective, because if increasing the thickness of the metal level being initially formed, then adds by spraying process shape after spray coating The thickness of the metal level become.If by use electroless plating method etc. formed on anode material surface metal level such as so that Growth plated film, the most preferably by anode material immersing palladium chloride solution and filtering gains and form plated film.

Additionally, it is possible to, after forming multiple anode active material particles by spraying process etc., subsequently by making Metal level is formed with electrolytic plating method etc..In this case, plated film mainly along the superficial growth of anode active material particles, Gap between anode active material particles is formed metal level.In the situation subsequently forming metal level, it is possible to, can Make formation anode active material particles and then form the step repeated several times of metal level.Such as, at active material of positive electrode In the relatively large situation in ideal thickness ground of grain, such forming method is effective, because being repeatedly formed anode activity material Material granule and metal level, and define the metal level of q.s, even if the gross thickness of anode active material particles is big.

The description of the detailed construction example of anode will be provided.

Fig. 2 A to Fig. 6 B shows the amplifier section of anode shown in Fig. 1.Fig. 2 A, 3A, 5A and 6A show the SEM in cross section Photo (secondary electron image), Fig. 2 B, 3B, 5B and 6B show the schematic diagram of SEM image shown in Fig. 2 A, 3A, 5A and 6A.Figure 4 SEM photograph showing surface.Fig. 2 A to 4 shows the situation using elementary silicon as active material of positive electrode.Fig. 5 A to 6B shows Show the situation that active material of positive electrode is the material with silicon and metallic element.

By such as forming anode active material layers with spraying process deposition anode material on the surface of anode collector 1 2.Anode active material layers 2 comprises multiple particulate anodes active material (anode active material particles 201).As at Fig. 2 A to 3B Shown in, anode active material particles 201 can have the multiple structure of the thickness direction stacking along anode active material layers 2. Additionally, as fig. 5 a and fig. 5b, anode active material particles 201 can have the surface layout along anode collector 1 Single layer structure.

Such as, as shown in Fig. 2 A to 3B, anode active material layers 2 has wherein anode active material particles 201 and sun Pole collector 1 contact part (contact portion P1) and wherein anode active material particles 201 do not contact with anode collector 1 Part (non-contact part P2).It addition, anode active material layers 2 has multiple space 2K.

As shown in Fig. 2 A to 6B, multiple anode active material particles 201 comprise spheroidal particle 201X and aspherical particle 201Y.In the situation from surface observation anode active material layers 2, spheroidal particle 201X be rendered as having sub-circular profile or The granule of approximate ellipsoidal profile, and aspherical particle 201Y is rendered as the granule with polygonal profile or sheet profiles.Cause This, in SEM image, spheroidal particle 201X can clearly distinguish with aspherical particle 201Y.

At least partly aspherical particle 201Y is such as flat.I.e., as shown in Figure 3A and 3B, multiple aspherical particles 201Y comprises flat particle 201YP.Flat particle 201YP is contacted by stacking with adjacent anode active material particles 201.

In the situation that anode active material particles 201 has silicon and metallic element, such as, segment anode active material Grain 201 has silicon and metallic element.In this case, the state of anode active material particles 201 can be alloy state Or compound (being separated) state (SP) (AP).Only there is silicon but not there is anode active material particles 201 institute of metallic element The state at place is elemental stage (MP).

These three crystal state (MP, AP and SP) is clearly illustrated in Fig. 5 A and Fig. 5 B.I.e., it was observed that elemental stage (MP) anode active material particles 201 is uniform grey region.Observe the anode active material particles of alloy state (AP) 201 is flat-white region.Observe that the anode active material particles 201 of phase-separated state (SP) is for wherein grey parts and white The region of color part mixing.

The most as shown in Figure 6A and 6B, in the anode active material layers 2 gap between anode active material particles 201 There is metal level 202.Metal level 202 is such as present in by being provided to cover the surface of anode active material particles 201 In aforementioned gap.In which case it is preferred to provide metal level 202 to cover the upper space being positioned at anode active material layers 2 Anode active material particles 201 in Ceng.At least partly metal level 202 can be the alloy containing silicon.

The definition (calculation procedure) of the thickness of metal level 202 is as follows.First, it is thus achieved that anode active material layers 2 and metal level The SEM photograph (Fig. 6 A) in the cross section of 202, described anode active material layers 2 comprises multiple anode active material particles 202.Subsequently, Given position in SEM photograph draws vertical line L (being perpendicular to the line on the surface of anode collector 1).Afterwards, measure and vertical line L The distance (thickness) of the metal level 202 of traversed by.In the situation shown in Fig. 6 B, (some P1 is extremely at 3 points for metal level 202 and vertical line L P3) traversed by.Therefore, after measuring the thickness of metal level 202 of each point, it is thus achieved that its summation.Subsequently, drafting vertical line L is being changed Position while, by obtain metal level 202 thickness (summation) aforementioned operation repeat 50 times.In this case, can appoint Meaning ground (randomly) changes the position drawing vertical line L.But, determine position the most regularly, preferably paint with the interval of 5 μm Vertical line L processed.Finally, the meansigma methods of metal level 202 thickness obtained is calculated 50 times.

Such as, anode is manufactured by following operation.

First, the anode collector 1 being made up of the electrolytic copper foil etc. being roughened is prepared.Subsequently, by using spraying process to exist On the surface of anode collector 1, deposition has silicon and as the material (as anode material) of constituent element thus forms active material of positive electrode Layer 2.In this case, spraying melting state or the anode material of semi-molten shape body, thus on the surface of anode collector 1 Deposition anode material.Therefore, the anode active material layers 2 of formation is containing multiple crystalline state anode active material particles (spheroidal particle And aspherical particle).Therefore, anode is completed.

In the situation being formed anode active material layers 2 by use spraying process, for instance, it is possible to by regulation anode material Particle diameter, material quality, input quantity and fusion temperature, the amount of material supply gas, the chilling temperature etc. of base material, change The number of spheroidal particle, its particle diameter (median size) and its circularity.

According to this anode, anode active material layers 2 has the silicon crystalline state active material of positive electrode as constituent element containing multiple Grain.The plurality of anode active material particles comprises spheroidal particle and aspherical particle.In this case, live compared to anode Property material is amorphous situation, and the physical property of anode active material particles deteriorated little with the working time.It addition, phase Ratio does not comprise the situation of spheroidal particle in anode active material particles, and anode active material layers 2 is the most swollen when electrode reaction Swollen and shrink, therefore anode collector 1 deforms hardly.Therefore, this anode can aid in the performance improving electrochemical appliance. More specifically, at this anode in the situation of secondary cell, this anode can aid in and improves cycle characteristics and expansion characteristics.

Especially, if diffraction maximum in (111) crystal face of the anode active material particles obtained by X-ray diffraction Half-peak breadth (2 θ) is 20 degree or less, or the crystallite dimension coming from this crystal face is 10nm or bigger, then be obtained in that higher Effect.If it addition, the median size of spheroidal particle is 0.5 μm-35 μm (including two end values), if or spheroidal particle Circularity is 0.5-1 (including two end values), then be obtained in that higher effect.

If additionally, it is 1.5 former that anode active material particles has the oxygen content in oxygen and anode active material particles Sub-%-40 atom % (includes two end values), if or anode active material particles there is metallic element such as ferrum, then can Obtain higher effect.Similarly, if anode active material layers 2 has high oxygen-containing region and low oxygen-containing region, then can obtain Effect that must be higher.

If it addition, the surface of anode collector 1 is roughened, it is possible to improve anode collector 1 and active material of positive electrode Contact performance between layer 2.In this case, if 10 mean roughness Rz on anode collector 1 surface be 1.5 μm or Bigger or preferably 3 μm-30 μm (including two end values), then be obtained in that higher effect.

If it addition, the gap that anode active material layers 2 is between anode active material particles has metal level 202, Then can improve cycle characteristics further.In this case, if metal level 202 covers anode active material particles 201 Surface, then be obtained in that higher effect.

2. use the electrochemical appliance (secondary cell) of anode

It follows that by the description of the use embodiment that provides aforesaid anode.In this description, using secondary cell as electrification Learn the embodiment of device.It is used as follows aforesaid anode.

The first secondary cell of 2-1. (square)

Fig. 7 and Fig. 8 shows the cross section structure of the first secondary cell.Fig. 8 shows along the VIII-shown in Fig. 7 The cross section that VIII line is taken.Secondary cell described herein is wherein embedding based on the lithium ion as electrode reaction thing With the lithium rechargeable battery taking off the capacity representing anode 22.

The overall structure of secondary cell

In this secondary cell, in battery case 11, main receiving has the cell device 20 of flat wound winding-structure.

Battery case 11 is such as square package element.As shown in Figure 8, this square potted element has and in longitudinal cross-section is Rectangle or the shape of approximate rectangular (including partial trace).This square potted element does not merely comprise the rectangular cell of rectangular shape, And constitute the rectangular cell of elliptical shape.That is, this square potted element represents the rectangular vessel linear element with bottom, or Having the elliptical vessel linear element of bottom, it is respectively provided with rectangular shape or the approximation formed by being connected circular arc by straight line The opening of rectangular shape (elliptical shape).Fig. 8 shows that battery case 11 has the situation of rectangular cross sectional shape.Including aforementioned electricity The battery structure of pond shell 11 is so-called square structure.

Battery case 11 is made up of such as ferrum, aluminum or their alloy etc..In some cases, battery case 11 also has conduct The effect of electrode terminal.Especially, for by utilizing the rigidity of battery case 11 (the most deformable characteristic) to prevent charging Expanding with secondary cell during electric discharge, the ferrum of rigidity is than aluminum more preferably.In the situation that battery case 11 is fabricated from iron, battery case 11 can To carry out plating with such as nickel etc..

It addition, battery case 11 has hollow structure, wherein one end of battery case 11 is unlimited, and another of battery case 11 End is to close.At the opening of battery case 11, connect insulation board 12 and battery cover 13, thus by airtight for the inside of battery case 11 Seal.Insulation board 12 is between cell device 20 and battery cover 13, and the screw winding side face being perpendicular to cell device 20 is arranged, And it is made up of such as polypropylene etc..Battery cover 13 is made up of the material being such as similar to battery case 11, and can be such as battery Shell 11 equally plays the effect of electrode terminal.

Outside at battery cover 13, it is provided that terminal board 14 is as cathode terminal.Terminal board 14 and battery cover 13 are by therebetween Insulation shell (insulating case) 16 electric insulation in addition.Insulation shell 16 is made up of such as polybutylene terephthalate etc.. It addition, the approximate center at battery cover 13 provides through hole.Negative electrode pin 15 is inserted in this through hole and negative electrode pin is electrically connected to Terminal board 14, and with battery cover 13 by packing ring 17 electric insulation in addition therebetween.Packing ring 17 is made up of such as insulant, and And its surface scribbles such as Colophonium.

Adjacent edges at battery cover 13, it is provided that split valve 18 and hand-hole 19.The valve 18 that splits is electrically connected to battery cover 13. The interior pressure making battery wherein due to internal short-circuit, external heat etc. becomes, in the situation of certain level or bigger, splitting Valve 18 separates with battery cover 13 with pressure in release.Hand-hole is sealed by the sealing member 19A being made up of such as stainless steel ball etc. 19。

Formed by stacking negative electrode 21 and anode 22 and spacer body therebetween 23 and screw winding gained laminated body Cell device 20.According to the shape of battery case 11, cell device 20 is flat pattern.The cathode leg 24 being made up of aluminum etc. is connected It is connected to the end (such as, end in it) of negative electrode 21.The anode tap 25 being made up of nickel etc. is connected to the end (example of anode 22 As, its outer end).Cathode leg 24 is electrically connected to terminal board 14 by being soldered to the end of negative electrode pin 15.Welding anode draws Line 25, and it is electrically connected to battery case 11.

Negative electrode

In negative electrode 21, such as, cathode active material 21B provides at two of the cathode current collector 21A with an opposite On individual face.But, cathode active material 21B can be provided in only on single of cathode current collector 21A.

Cathode current collector 21A is made up of such as aluminum, nickel or rustless steel etc..

Cathode active material 21B contains one or more as active material of cathode and can embed and deviate from lithium ion Cathode material.As required, cathode active material 21B can comprise other material such as cathode adhesive and negative electrode conduction Agent.

As cathode material, preferably lithium-containing compound, this is because it is possible to obtain high-energy-density.Lithium-containing compound Example include the composite oxides that there is lithium and transition metal as constituent element, containing lithium and transition metal as group The phosphate compounds of unit.In particular it is preferred at least one comprised in cobalt, nickel, manganese and ferrum is as the change of transition metal Compound, this is because thereby is achieved higher voltage.Its chemical formula is by such as Li_XM1O₂Or Li_yM2PO₄Represent.In this formula In, M1 and M2 represents one or more transition metals.The value of x and y changes according to charging and discharging state, and generally It is 0.05≤x≤1.10 and 0.05≤y≤1.10.

The example of the composite oxides with lithium and transition metal includes lithium cobalt composite oxide (Li_XCoO₂), lithium nickel Composite oxides (Li_XNiO₂) and the lithium nickel composite oxide that represented by formula 12.There is the phosphatization of lithium and transition metal The example of compound includes lithium iron phosphate compound (LiFePO₄), ithium iron manganese phosphate compounds (LiFe_1-uMn_uPO₄(u ＜ 1)), this is because be derived from high battery capacity and excellent cycle characteristics.

Formula 12

LiNi1_1-xM_xO₂

In the formula, M be cobalt, manganese, ferrum, aluminum, vanadium, stannum, magnesium, titanium, strontium, calcium, zirconium, molybdenum, technetium, ruthenium, tantalum, tungsten, rhenium, ytterbium, copper, At least one in zinc, barium, boron, chromium, silicon, gallium, phosphorus, antimony and niobium.X is 0.005 ＜ x ＜ 0.5.

It addition, the example of cathode material includes oxide, disulphide, chalcogenide and conducting polymer.Oxide Example includes titanium oxide, vanadium oxide and manganese dioxide.The example of disulphide includes titanium disulfide and molybdenum sulfide.Chalcogenide Example includes selenizing niobium.The example of conducting polymer includes sulfur, polyaniline and polythiophene.

Self-evident, cathode material can be the material in addition to above-claimed cpd.Furthermore it is possible to made by arbitrarily mixing By two or more in above-mentioned cathode material.

The example of cathode adhesive includes synthetic rubber such as butadiene-styrene rubber, Viton and ethylene propylene diene rubber；Polymerization Thing material such as Kynoar.Can be used alone one therein, or can use therein multiple by mixing.

The example of negative electrode conductive agent includes material with carbon element such as graphite, white carbon black, acetylene black and Ketjen black (Ketjen black).Can be used alone such material with carbon element, or can be therein multiple by being used in mixed way.Negative electrode conductive agent is permissible It is metal material, conducting polymer etc., as long as this material has electric conductivity.

Anode

In anode 22, such as, anode active material layers 22B provides in two of anode collector 22A with an opposite On individual face.Anode collector 22A and anode active material layers 22B are similar to that aforesaid anode Anodic collector 1 and sun The structure of pole active material layer 2.Anode active material layers 22B comprises spheroidal particle and aspherical particle as the plurality of anode Active material particle.In anode 22, it is possible to embed and the chargeable capacity deviate from the anode material of lithium ion preferably greater than The discharge capacity of negative electrode 21.

Fig. 9 shows negative electrode 21 shown in Fig. 8 and the planar structure of anode 22.In fig .9, cathode active material 21B Forming range in negative electrode 21 shade in addition, and the forming range that anode active material layers 22B is in anode 22 is the most cloudy Shadow.

In this secondary cell, such as, the part surface at cathode current collector 21A is provided as cathode active material 21B Time upper (such as, along longitudinally central region), anode active material layers 22B provides the whole table in anode collector 22A On face.That is, anode active material layers 22B provides the region relative with cathode active material 21B in anode collector 22A In (opposed area R1) or with cathode active material 21B therein not relative to region in (non-relative region R2).This In situation, outside anode active material layers 22B, the part provided in opposed area R1 contributes to charging and discharging reaction, The part provided in non-relative region R2 contributes to charging and discharging reaction hardly.

Live as it has been described above, anode active material layers 22B has spheroidal particle and aspherical particle as the plurality of anode Property material granule.But, if anode active material layers 22B expands when charging and discharging and shrinks, as a result of which it is, spherical Grain and aspherical particle deformable or destruction.In this case, non-relative region R2 is not reacted by charging and discharging and is affected, And keep constant forming anode active material layers 22B state immediately after.Therefore, when checking the presence or absence of spheroidal particle, grain During footpath etc., preferably check anode active material layers 22B in non-relative region R2, this is because it is possible to well to repeat Mode check that the presence or absence etc. of spheroidal particle does not relies on charging and discharging experience.

Spacer body

Spacer body 23 is spaced apart with anode 22 by negative electrode 21, and makes lithium ion pass through and prevent by two electrodes simultaneously The short circuit that contact produces.Spacer body 23 is by such as being constituted many by synthetic resin (such as politef, polypropylene and polyethylene) Pore membrane or ceramic porous membrane etc. are made.Spacer body 23 can be the lamilated body being made up of two or more perforated membranes.

Electrolyte

Electrolysis immersion as liquid electrolyte is contained in spacer body 23.Electrolyte contains solvent and is dissolved in therein Electrolytic salt.

Solvent comprises such as one or more nonaqueous solvents such as organic solvent.Can solvent the most described below.

The example of nonaqueous solvent includes as follows.That is, its example include ethylene carbonate, propylene carbonate, butylene carbonate, Dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate, methyl propyl carbonate, gamma-butyrolacton, gamma-valerolactone, 1,2-dimethoxy Ethane and oxolane.Its other example includes 2-methyltetrahydrofuran, Pentamethylene oxide., DOX, 4-methyl isophthalic acid, 3-dioxolanes, 1,3-dioxane and Isosorbide-5-Nitrae-dioxane.Additionally, its example includes methyl acetate, ethyl acetate, propanoic acid first Ester, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethylacetate and tri-methyl ethyl acetate.Additionally, its example bag Include acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, DMF, N-Methyl pyrrolidone With N-methyloxazolidinone.Additionally, its example includes N, N '-dimethyl imidazolone, nitromethane, nitroethane, sulfolane, Trimethyl phosphate and dimethyl sulfoxide.

In particular it is preferred in ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and Ethyl methyl carbonate At least one.In which case it is preferred to high viscosity (high-k) solvent (such as, DIELECTRIC CONSTANT ε >=30) such as carbon Acid ethyl and propylene carbonate and low viscosity solvent (such as, viscosity≤1mPa s) such as dimethyl carbonate, Ethyl methyl carbonate Combination with diethyl carbonate.Thus improve dissociation properties and the ionic mobility of electrolytic salt.

Especially, solvent preferably comprises and has halogen as the tool shown in the linear carbonate of constituent element and formula 2 shown in formula 1 There is halogen as at least one in the cyclic carbonate of constituent element.Thus, when charging and discharging on the surface of anode 22 shape Become stable protecting film, and prevent the decomposition of electrolyte.Its content (being used alone or being used in mixed way) in a solvent is not subject to Specific restriction, but for example, it is preferable to be 0.01 weight %-50 weight % (including two end values).R11 to R16 in formula 1 can phase Same or different.This is equally applicable to the R17 to R20 in formula 2.

Formula 1

In the formula, R11 to R16 is hydrogen, halogen, alkyl or haloalkyl.At least one in R11 to R16 is halogen Or haloalkyl.

Formula 2

In the formula, R17 to R20 is hydrogen, halogen, alkyl or haloalkyl.At least one in R17 to R20 is halogen Or haloalkyl.

The type of halogen is not particularly limited, but particularly preferably fluorine, chlorine or bromine, and more preferably fluorine, this is because with Other halogen is compared and be thereby is achieved higher effect.The number of halogen is more preferably 2 compared with 1, and also can be 3 Or more, this is because hence improve the ability forming protecting film, and define more rigidity and stable protecting film. Therefore, the decomposition reaction of electrolyte is more prevented.

The example of the linear carbonate with halogen shown in formula 1 includes fluoromethyl methylcarbonate, double (methyl fluorides) Carbonic ester and carbonic acid difluoromethyl methyl ester.Can be used alone one therein, or can be therein by being used in mixed way Multiple.

The example of the cyclic carbonate with halogen shown in formula 2 includes the compound shown in following formula 2-1 to 2-21. Can be used alone one therein, or can be therein multiple by being used in mixed way.

Formula 2-1 to 2-12

Formula 2-13 to 2-21

In particular it is preferred to the 4-fluoro-1,3-dioxolan-2-one shown in formula 2-1 or 4 shown in formula 2-3,5-bis- Fluoro-1,3-dioxolan-2-one, and more preferably the latter.Particularly as latter compound, transisomer ratio is cis Isomer is more preferably, this is because transisomer is easily obtained and provides high effect.

Solvent preferably comprises at least one in the cyclic carbonate with unsaturated carbon bond shown in formula 3 to formula 5.From And, on the surface of anode 22, form stable protecting film when charging and discharging, and therefore prevent the decomposition of electrolyte.Its The content (being used alone or being used in mixed way) in solvent is not particularly limited, but for example, it is preferable to is 0.01 weight %-10 weight % (including two end values).

Formula 3

In the formula, R21 and R22 is hydrogen or alkyl.

Formula 4

In the formula, R23 to R26 is hydrogen, alkyl, vinyl or aryl.At least one in R23 to R26 is vinyl Or aryl.

Formula 5

In the formula, R27 is alkylidene.

The cyclic carbonate with unsaturated carbon bond shown in formula 3 is vinylene carbonate ester compounds.Vinylene carbonate The example of ester compounds includes following compounds.That is, its example includes vinylene carbonate (1,3-dioxole-2- Ketone), methyl vinylene (4-methyl isophthalic acid, 3-dioxole-2-ketone) and carbonic acid ethyl vinylene (4-second Base-1,3-dioxole-2-ketone).It addition, its example includes 4,5-dimethyl-1,3-dioxole-2- Ketone, 4,5-diethyl-1,3-dioxole-2-ketone, 4-fluoro-1,3-dioxole-2-ketone and 4-fluoroform Base-1,3-dioxole-2-ketone.In particular it is preferred to vinylene carbonate, this is because vinylene carbonate is prone to obtain High effect must and be provided.

The cyclic carbonate with unsaturated carbon bond shown in formula 4 is vinyl ethylene carbonate compound.Ethylene The example of thiazolinyl ethyl compound includes following compounds.That is, its example include vinyl ethylene carbonate (4-vinyl- DOX-2-ketone), 4-methyl-4-vinyl-DOX-2-ketone and 4-ethyl-4-vinyl-1,3-bis- Butyl oxide link-2-ketone.Its other example includes 4-n-pro-pyl-4-vinyl-DOX-2-ketone, 5-methyl-4-ethylene Base-DOX-2-ketone, 4,4-divinyl-DOX-2-ketone and 4,5-divinyl-1,3-dioxy penta Ring-2-ketone.In particular it is preferred to vinyl ethylene carbonate, this is because vinyl ethylene carbonate is easily obtained, and provide High effect.Self-evident, all of R23 to R26 can be vinyl or aryl.Additionally, some in R23 to R26 are permissible It is vinyl, and wherein other is aryl.

The cyclic carbonate with unsaturated carbon bond shown in formula 5 is carbonic acid methylene ethyl compound.Carbonic acid is sub- The example of methyl ethyl compound includes following compounds.That is, its example include 4-methylene-DOX-2-ketone, 4,4-dimethyl-5-methylene-DOX-2-ketone and 4,4-diethyl-5-methylene-DOX-2-ketone. Carbonic acid methylene ethyl compound can have 1 methylene (compound shown in formula 5) or have 2 methylene.

In addition to the compound shown in formula 3 to formula 5, the cyclic carbonate with unsaturated carbon bond can also is that have phenyl ring Catechol carbonic ester etc..

It addition, solvent preferably comprises sultone (cyclic sulfonic acid ester), this is because improve the change of electrolyte the most further Learn stability.As sultone, such as, citation is propane sultone, propene sultone etc..Can be used alone such sulphur Lactone, or can be therein multiple by being used in mixed way.The content of sultone for example, 0.5 weight %-5 weight % in solvent (including two end values).

It addition, solvent is preferably containing anhydride, because improving the chemical stability of electrolyte the most further.The example bag of anhydride Include carboxylic acid anhydrides, disulfonic acid acid anhydride and carboxylic acid and the anhydride of sulfonic acid.The example of carboxylic acid anhydrides includes succinic anhydride, glutaric anhydride and Malaysia Acid anhydride.The example of disulfonic acid acid anhydride includes ethane disulfonic acid acid anhydride and propanedisulfonic acid acid anhydride.The example bag of the anhydride of carboxylic acid and sulfonic acid Include sulfosalicylic acid acid anhydride, Sulfo propionic acid acid anhydride and sulfo group butyryl oxide..Can be used alone described anhydride, or can be made by mixing With therein multiple.The content of anhydride for example, 0.5 weight %-5 weight % (including two end values) in solvent.

Electrolytic salt contains such as-kind or multiple light metal salt such as lithium salts.Can electrolyte the most described below Salt.

The example of lithium salts includes following.That is, its example includes lithium hexafluoro phosphate, LiBF4, lithium perchlorate and hexafluoro Arsenic acid lithium.It addition, its example includes tetraphenylboronic acid lithium (LiB (C₆H₅)₄), Loprazolam lithium (LiCH₃SO₃), fluoroform sulphur Acid lithium (LiCF₃SO₃) and tetrachloro-lithium aluminate (LiAlCl₄).Its other example includes hexafluorosilicic acid two lithium (Li₂SiF₆), chlorination Lithium (LiCl) and lithium bromide (LiBr).

Especially, more preferably at least one in lithium hexafluoro phosphate, LiBF4, lithium perchlorate and hexafluoroarsenate lithium, And more preferably lithium hexafluoro phosphate, this is because reduce internal resistance, and is derived from higher effect.

Especially, electrolytic salt preferably comprises at least one shown in formula 6 to formula 8 in compound, this is because thus Obtain higher effect.R31 and R33 in formula 6 can be identical or different.This be equally applicable to the R41 to R43 in formula 7 and R51 and R52 in formula 8.

Formula 6

In the formula, 1 race's element during X31 is long formula periodic chart or 2 race's element or aluminum.M31 be transition metal, 13 race's elements, 14 race's elements or 15 race's elements in long formula periodic chart.R31 is halogen.Y31 is-(O=) C-R32-C (= O)-,-(O=) C-C (R33)₂-or-(O=) C-C (=O)-.R32 is alkylidene, halogeno alkylen, arlydene or halo Asia virtue Base.R33 is alkyl, haloalkyl, aryl or halogenated aryl.A3 is one in integer 1-4.B3 is 0,2 or 4.c3、d3、m3 It it is one in integer 1-3 with n3.

Formula 7

In the formula, 1 race's element during X41 is long formula periodic chart or 2 race's elements.M41 is transition metal, long formula week 13 race's elements, 14 race's elements or 15 race's elements in phase table.Y41 is-(O=) C-(C (R41)₂)_b4-C (=O)-,-(R43)₂C- (C(R42)₂)_c4-C (=O)-,-(R43)₂C-(C(R42)₂)_c4-C(R43)₂-、-(R43)₂C-(C(R42)₂)_c4-S (=O)₂-、- (O=)₂S-(C(R42)₂)_d4-S (=O)₂-or-(O=) C-(C (R42)₂)_d4-S (=O)₂-.R41 and R43 is hydrogen, alkyl, halogen Element or haloalkyl.At least one in R41 and R43 is halogen or haloalkyl respectively.R42 is hydrogen, alkyl, halogen or halo Alkyl.A 4, e4 and n4 are the integers of 1 or 2.B4 and d4 is one in integer 1-4.C4 is one in integer 0-4.F4 and M4 is one in integer 1-3.

Formula 8

In the formula, 1 race's element during X51 is long formula periodic chart or 2 race's elements.M51 is transition metal, long formula week 13 race's elements, 14 race's elements or 15 race's elements in phase table.Rf be carbon number be 1-10 (including two end values) fluorinated alkyl or Carbon number is the fluoro aryl of 1-10 (including two end values).Y51 is-(O=) C-(C (R 51)₂)_d5-C (=O)-,-(R52)₂C- (C(R51)₂)_d5-C (=O)-,-(R52)₂C-(C(R51)₂)_d5-C(R52)₂-、-(R52)₂C-(C(R51)₂)_d5-S (=O)₂-、- (O=)₂S-(C(R51)₂)_e5-S (=O)₂-or-(O=) C-(C (R51)₂)_e5-S (=O)₂-.R51 is hydrogen, alkyl, halogen or halogen Substituted alkyl.R52 is hydrogen, alkyl, halogen or haloalkyl, and at least one in them is halogen or haloalkyl.a5、f5 It is 1 or 2 with n5.B5, c5 and e5 are one in integer 1-4.D5 is one in integer 0-4.G5 and m5 is in integer 1-3 One.

1 race's element representation hydrogen, lithium, sodium, potassium, rubidium, caesium and francium.2 race's element representation berylliums, magnesium, calcium, strontium, barium and radium.13 units of race Element represents boron, aluminum, gallium, indium and thallium.14 race's element representation carbon, silicon, germanium, stannum and lead.15 race's element representation nitrogen, phosphorus, arsenic, antimony and Bismuth.

The example of compound shown in formula 6 includes that formula 6-1 is to the compound shown in formula 6-6.Compound shown in formula 7 Example includes that formula 7-1 is to the compound shown in formula 7-8.Shown in formula 8, the example of compound includes the chemical combination shown in formula 8-1 Thing.Self-evident, compound is not limited to aforesaid compound, and this compound can be other compound, so long as chemical combination Thing has the structure shown in formula 6 to formula 8.

Formula 6-1 to 6-6

Formula 7-1 to 7-8

Formula 8-1

It addition, electrolytic salt can be with at least one in compound shown in contained 9 to formula 11.Because being derived from relatively High effect.M and n in formula 9 can be identical or different.This is equally applicable to p, q and the r in formula 11.

Formula 9

LiN(C_mF_2m+1SO₂)(C_nF_2n+1SO₂)…(9)

In the formula, m and n is the integer of 1 or bigger.

Formula 10

In the formula, R61 be carbon number be the perfluorinated alkylidene of the straight chain/side chain of 2-4 (including two end values).

Formula 11

LiC(C_pF_2p+1SO₂)(C_qF_2q+1SO₂)(C_rF_2r+1SO₂)…(11)

In the formula, p, q and r are the integers of 1 or bigger.

Chain imide compound shown in formula 9 includes following compound.That is, its example includes double (fluoroform sulphur Acyl group) imine lithium (LiN (CF₃SO₂)₂) and double (pentafluoroethane sulfonyl) imine lithium (LiN (C₂F₅SO₂)₂).It addition, its example Including (trifluoromethane sulfonyl group) (pentafluoroethane sulfonyl) imine lithium (LiN (CF₃SO₂)(C₂F₅SO₂)).It addition, its example bag Include (trifluoromethane sulfonyl group) (heptafluoro-propane sulfonyl) imine lithium (LiN (CF₃SO₂)(C₃F₇SO₂)).It addition, its example includes (trifluoromethane sulfonyl group) (nine fluorine butane sulfonyls) imine lithium (LiN (CF₃SO₂)(C₄F₉SO₂)).Can be used alone in them One, or can be multiple by be used in mixed way in them.

The example of the cyclic imide compound shown in formula 10 is the compound shown in facial 10-1 to 10-4 under including. Can be used alone one therein, or can be therein multiple by being used in mixed way.

Formula 10-1 to 10-4

The example of chain methide (methyde) compound shown in formula 11 includes three (trifluoromethane sulfonyl group) first Base lithium (LiC (CF₃SO₂)₃)。

Electrolytic salt is preferably 0.3mol/kg-3.0mol/kg (including two end values) relative to the content of solvent, and this is Because being derived from high ionic conductivity.

The work of secondary cell

In this secondary cell, when charging, such as, lithium ion is deviate from from negative electrode 21, and is contained in spacer body via leaching Electrolyte in 23 is embedded in anode 22.Meanwhile, when electric discharge, such as, lithium ion is deviate from from anode 22, and contains via leaching Electrolyte in spacer body 23 is embedded in negative electrode 21.

The method manufacturing secondary cell

Such as, secondary cell is manufactured by following operation.

First, negative electrode 21 is formed.First, active material of cathode, cathode adhesive and negative electrode conductive agent are mixed To prepare cathode mix, it is dispersed in organic solvent forming pasty state cathode mixture slurry.Subsequently, scraped by use Cutter, bar coaters etc., be evenly coated with two faces of cathode current collector 21A with this cathode mixture slurry, be dried from And form cathode active material 21B.Finally, by using roll squeezer etc. that cathode active material 21B is compressed molding, Heat the most simultaneously.In this case, can by gains compression forming several times.

Then, anode 22 is formed according to the operation of above-mentioned formation anode.In this case, in the two of anode collector 22A Define on individual face and comprise the spheroidal particle as multiple anode active material particles and the active material of positive electrode of aspherical particle Layer 22B.

By following secondary cell for assembling.First, after cell device 20 is contained in battery case 11, by insulation board 12 It is arranged on cell device 20.Subsequently, by welding etc. cathode leg 24 is connected to negative electrode pin 15, and will by welding etc. Anode tap 25 is connected to battery case 11.Afterwards, by laser welding etc., battery cover 13 is fixed on the opening of battery case 11. Finally, electrolyte is injected into battery case 11 from hand-hole 19, and leaching is contained in spacer body 23.Thereafter, sealing member is passed through 19A seals hand-hole 19.Thus complete the secondary cell shown in Fig. 7 and Fig. 8.

According to the first secondary cell, anode 22 has the structure being similar to above-mentioned anode.Therefore, at charging and discharging Time, the physical property of anode active material particles deteriorated little with the working time, and anode collector 22A is almost unchanged Shape.Therefore, the cycle characteristics of excellence and excellent expansion characteristics will be obtained in that.

Especially, the solvent at electrolyte comprise the linear carbonate with halogen, the cyclic carbonate with halogen, tool Have in the situation of the cyclic carbonate of unsaturated carbon bond, sultone or anhydride, it is possible to improve cycle characteristics further.

It addition, the electrolytic salt at electrolyte comprises lithium hexafluoro phosphate, LiBF4, lithium perchlorate and hexafluoroarsenate lithium In at least one；Or in the situation of the compound shown in formula 6 to formula 11, it is possible to improve cycle characteristics further.

2-2. the second secondary cell (column type)

Figure 10 and Figure 11 shows the cross section structure of the second secondary cell.Figure 11 shows the screw winding shown in Figure 10 The amplifier section of electrode body 40.

This secondary cell is such as the lithium rechargeable battery of the first secondary cell aforementioned.This secondary cell is in approximation hollow Spiral winding electrode 40 and a pair insulation board 32 and 33 is accommodated in the battery case 31 of cylindrical shape.Use such electricity The battery structure of pond shell 31 is so-called column type.

Battery case 31 is made by being such as similar to the material of battery case 11 in the first secondary cell.One end of battery case 31 Open wide, and the other end of battery case 31 is to close.A pair insulation board 32 and 33 is vertically arranged as by spiral winding electrode 40 Between being clipped in, and it is arranged perpendicularly to the extension of screw winding outer peripheral face.

At the opening of battery case 31, battery cover 34, and provide in the relief valve mechanism 35 and PTC within battery cover 34 (positive temperature coefficient) device 36 is by connecting with packing ring 37 caulked.Processed by this caulked, by airtight for the inside of battery case 31 Seal.Battery cover 34 is made up of the material being such as similar to battery case 31.Relief valve mechanism 35 is electrically connected to by PTC device 36 Battery cover 34.In relief valve mechanism 35, fade to certain level or more making interior pressure due to internal short-circuit, external heat etc. In big situation, discoid plate 35A inverted arch thus cut off the electrical connection between battery cover 34 and spiral winding electrode 40.In temperature During rising, PTC device 36 makes resistance increase, thus limits electric current to prevent the abnormal delivery in hot weather by high-current leading raw.Packing ring 37 It is made up of such as insulant.The surface of packing ring 37 scribbles such as Colophonium.

In spiral winding electrode 40, stacking spiral shell together with spacer body 43 between the two by negative electrode 41 and anode 42 Circumvolution around.Such as, centrepin 44 is inserted the center of spiral winding electrode 40.In spiral winding electrode 40, by aluminum etc. The cathode leg 45 made is connected to negative electrode 41, and the anode tap 46 being made up of nickel etc. is connected to anode 42.Anode tap 45 leads to Cross and be such as welded to relief valve mechanism 35 and be electrically connected to battery cover 34.Anode tap 46 such as welds, thus electrically connects To battery case 31.

Negative electrode 41 has the most such structure, and in the structure shown here, cathode active material 41B provides has an opposite Cathode current collector 41A two faces on.The structure of cathode current collector 41A and cathode active material 41B is analogous respectively to Cathode current collector 21A and the structure of cathode active material 21B in a kind of secondary cell.

Anode 42 has the most such structure, and in the structure shown here, anode active material layers 42B provides has an opposite Anode collector 42A two faces on.The structure of anode collector 42A and anode active material layers 42B is analogous respectively to A kind of secondary cell Anodic collector 22A and the structure of anode active material layers 22B.Anode active material layers 42B comprises work Spheroidal particle and aspherical particle for multiple anode active material particles.

The structure of spacer body 43 and the composition of electrolyte are analogous respectively to the structure of spacer body 23 in the first secondary cell Composition with electrolyte.

In this secondary cell, such as, when charging, lithium ion is deviate from from negative electrode 41, and is embedded into sun via electrolyte In pole 42.Meanwhile, such as, when electric discharge, lithium ion is deviate from from anode 42, and is embedded in negative electrode 41 via electrolyte.

Such as, secondary cell is manufactured by following operation.

First, such as, the operation similar with the operation forming negative electrode 21 and anode 22 in the first secondary cell is used, Negative electrode 41 is formed by forming cathode active material 41B on the two of cathode current collector 41A faces, and by anode Form anode active material layers 42B on two faces of collector 42A and form anode 42.Subsequently, by welding etc., negative electrode is drawn Line 45 is connected to negative electrode 41, and by welding etc., anode tap 46 is connected to anode 42.Subsequently, by negative electrode 41 and anode 42 Stacking screw winding together with spacer body 43 between the two, thus form spiral winding electrode 40.Afterwards, by centrepin 44 centers being inserted into spiral winding electrode 40.Subsequently, spiral winding electrode 40 is clipped in a pair insulation board 32 and 33 it Between, and be contained in battery case 31.In this case, the end of cathode leg 45 is soldered to relief valve mechanism 35, and will The end of anode tap 46 is soldered to battery case 31.Subsequently, inject the electrolyte in battery case 31, and leaching is contained in spacer body 43 In.Finally, at the opening of battery case 31, filled by self-contained battery lid 34, relief valve mechanism 35 and PTC with packing ring 37 caulked Put 36.Thus complete the secondary cell shown in Figure 10 and Figure 11.

According to this second secondary cell, anode 42 has the structure of the anode 22 being similar to the first secondary cell.Cause This, will be obtained in that the cycle characteristics of excellence and excellent expansion characteristics.Other effect of this secondary cell is similar to the first Those of secondary cell.

The third secondary cell of 2-3. (lamination membranous type)

Figure 12 shows the exploded perspective structure of the third secondary cell.Figure 13 shows along XIII-shown in Figure 12 The exploded cross-sectional that XIII line is taken.

This secondary cell is such as the lithium rechargeable battery of the first secondary cell aforementioned.In this secondary cell, mainly Ground, is contained in the spiral winding electrode 50 that cathode leg on it 51 is connected with anode tap 52 in film packaging part 60.Make It is so-called lamination membranous type with the battery structure of such packaging part 60.

Such as, cathode leg 51 and anode tap 52 are respectively from the inside of packaging part 60 leads in same direction Portion.But, cathode leg 51 and anode tap 52 are relative to the allocation position of spiral winding electrode 50, their lead direction Etc. being not particularly limited.Cathode leg 51 is made up of such as aluminum etc., and anode tap 52 is made by such as copper, nickel or rustless steel etc. Become.These materials are the most lamellar or netted.

Packaging part 60 is made up of laminate film, in this laminate film, such as by fused layers, metal level and sealer with this Order carries out stacking.In this case, such as, the respective outer edge of the fused layers of two films is by fusion, binding agent etc. It is bonded to each other so that fused layers and spiral winding electrode 50 are relative to each other.The example of fused layers includes by polyethylene, polypropylene Etc. the film made.The example of metal level includes aluminium foil.The example of sealer includes by nylon, polyethylene terephthalate The film that ester etc. are made.

Particularly as packaging part 60, preferably wherein by polyethylene film, aluminium foil and nylon membrane with the aluminum of this order stacking Laminate film.But, packaging part 60 can be by having the laminate film of other laminate structures, polymeric film such as polypropylene screen or metal Film replaces above-mentioned aluminum laminated film to make.

The bonding film 61 preventing extraneous air from entering is inserted into packaging part 60 and cathode leg 51, anode tap 52 it Between.Bonding film 61 is made up of the material relative to cathode leg 51 and anode tap 52 with contact performance.Such material Example includes, such as vistanex such as polyethylene, polypropylene, modified poly ethylene and modified polypropene.

In spiral winding electrode 50, negative electrode 53 and anode 54 are together with spacer body 55 between the two and electrolyte 56 Stacking screw winding.Its outermost perimembranous 57 is protected by by protecting band.

Negative electrode 53 has the most such structure, and in this structure, cathode active material 53B provides and has an opposite On two faces of cathode current collector 53A.The structure of cathode current collector 53A and cathode active material 53B is analogous respectively to first Plant cathode current collector 21A and the structure of cathode active material 21B in secondary cell.

Anode 54 has the most such structure, and in the structure shown here, anode active material layers 54B provides has an opposite Anode collector 54A two faces on.The structure of anode collector 54A and anode active material layers 54B is analogous respectively to A kind of secondary cell Anodic collector 22A and the structure of anode active material layers 22B.Anode active material layers 54B has work Spheroidal particle and aspherical particle for multiple anode active material particles.

Spacer body 55 is similar to that the structure of spacer body 23 in the first secondary cell.

Dielectric substrate 56 is the so-called gel electrolyte containing electrolyte and the polymer keeping electrolyte.Preferably gel Electrolyte, this is because obtain high ionic conductivity (such as, at room temperature for 1mS/cm or bigger) and be possible to prevent The liquid leakage of electrolyte.

The example of polymer includes as follows.That is, its example include polyacrylonitrile, Kynoar, politef, poly-six Fluoropropene, poly(ethylene oxide), poly(propylene oxide), polyphosphazene, polysiloxanes and polyvinyl fluoride.It addition, its example includes poly-acetic acid Vinyl acetate, polyvinyl alcohol, polymethyl methacrylate, polyacrylic acid, polymethylacrylic acid, butadiene-styrene rubber, nitrile rubber, polyphenyl Ethylene and Merlon.It addition, its example includes the copolymer of vinylidene and hexafluoropropene.Can be used alone these polymerizations One in thing, or can by be used in mixed way therein two or more.In particular it is preferred to Kynoar or partially Fluorothene and the copolymer of hexafluoropropene, because such polymer is electrochemically stable.

The composition of electrolyte is similar to the composition of electrolyte in the first secondary cell.But, as gel electrolyte Dielectric substrate 56 in, the solvent in electrolyte represents generalized concept, not only includes liquid flux but also includes dissociating electricity Solve the solvent with ionic conductivity of matter salt.Therefore, use in the situation of the polymer with ionic conductivity wherein, poly- Compound is also included within solvent.

Replace the gel electrolyte layer 56 that wherein electrolyte is kept by polymer, can directly use electrolyte.This In situation, electrolysis immersion is contained in spacer body 55.

In this secondary cell, when charging, such as, lithium ion is deviate from from negative electrode 53, and embedding via dielectric substrate 56 Enter in anode 54.Meanwhile, when electric discharge, such as, lithium ion is deviate from from anode 54, and embeds negative electrode 53 via dielectric substrate 56 In.

For example, it is possible to manufactured the secondary cell including gel electrolyte layer 56 by following three kinds of operations.

In the first manufacture method, first, such as, by similar with negative electrode 21 in the first secondary cell and anode 22 Formation process form negative electrode 53 and anode 54.Especially, alive by forming negative electrode on two faces of cathode current collector 53A Property material layer 53B and form negative electrode 53, and by two faces of anode collector 54A formed anode active material layers 54B and form anode 54.Subsequently, preparation comprises the precursor solution of electrolyte, polymer and solvent.Coating with this precursor solution After negative electrode 53 and anode 54, solvent is made to volatilize to form gel electrolyte 56.Subsequently, by welding etc., cathode leg 51 is connected It is connected to cathode current collector 53A, and by welding etc., anode tap 52 is connected to anode collector 54A.Subsequently, it will thus provide have electricity Solve the negative electrode 53 of matter layer 56 and anode 54 together with spacer body 55 between the two stacking screw winding to obtain lamilated body.It After, protection band 57 is adhered to its outermost perimembranous thus forms spiral winding electrode 50.Finally, such as, by screw winding After electrode body 50 is clipped between the membranaceous packaging part of two panels 60, by the outer edge of the bond package parts 60 such as heat fused, to encapsulate spiral shell Rotation rolled electrode bodies 50.Now, bonding film 61 is inserted between cathode leg 51, anode tap 52 and packaging part 60.Thus, Complete the secondary cell shown in Figure 12 and Figure 13.

In the second manufacture method, first, cathode leg 51 is connected to negative electrode 53, and anode tap 52 is connected to Anode 54.Subsequently, stacking screw winding together with spacer body 55 between the two by negative electrode 53 and anode 54.Afterwards, will protect Protecting band 57 adheres to its outermost perimembranous, thus forms the screw winding body of the precursor as spiral winding electrode 50.Subsequently, exist After screw winding body being clipped between the membranaceous packaging part of two panels 60, the outermost perimembranous in addition to side is glued by heat fused etc. Close to obtain pouch-shaped state, and screw winding body is contained in bag-shaped packaging part 60.Subsequently, preparation is containing electrolyte, work Electrolyte for monomer, polymerization initiator and other material such as polymerization inhibitor if desired for polymer raw material forms Material, is injected in bag-shaped packaging part 60.Afterwards, the opening of packaging part 60 is carried out hermetic seal by heat fused etc.. Finally, make monomer thermal polymerization to obtain polymer.Thus, form gel electrolyte layer 56.Therefore, this secondary cell is completed.

In the third manufacture method, in addition to all scribble the spacer body 55 of polymer first by two sides, by with upper State the identical mode of the second manufacture method form screw winding body and be contained in bag-shaped packaging part 60.As coating point The example of the polymer of spacer 55, including containing vinylidene as the polymer of component, i.e. homopolymer, copolymer and multi-component copolymer Thing.Its object lesson includes Kynoar, containing vinylidene and hexafluoropropene as the bipolymer of component, Yi Jihan There is vinylidene, hexafluoropropene and the CTFE terpolymer as component.As polymer, except above-mentioned containing inclined fluorine Outside ethylene is as the polymer of component, it is also possible to comprise one or more other polymer.Subsequently, electrolyte is prepared and by it It is injected in packaging part 60.Afterwards, by the opening of the sealed packages such as heat fused 60.Finally, heat gains, simultaneously will weight Thing applies to packaging part 60, and is contacted with negative electrode 53 and anode 54 by spacer body 55, and between making polymer be in.Thus, Will electrolysis immersion containing in polymer, and make Gelation thus form dielectric substrate 56.Therefore, this secondary is completed Battery.

In the third manufacture method, compared with the first manufacture method, it is suppressed that the expansion of secondary cell.It addition, In the third manufacture method, compared with the second manufacture method, stay electricity hardly as the monomer of polymer raw material, solvent etc. Solve in matter layer 56.It addition, the forming step of polymer is advantageously controlled.Therefore, at negative electrode 53/ anode 54/ spacer body 55 And sufficient contact performance can be obtained between dielectric substrate 56.

According to this third secondary cell, anode 54 has the knot of the anode 22 being similar to that the first secondary cell Structure.Therefore, it is possible to obtain excellent cycle characteristics and excellent expansion characteristics.Other effect of this secondary cell is similar to first Plant those effects of secondary cell.

Embodiment

Will be described in detail embodiments of the invention.

Embodiment 1-1 to 1-10

The lamination membranous type lithium rechargeable battery shown in Figure 12 and Figure 13 is manufactured by following operation.

First, negative electrode is formed by using painting method to form cathode active material 53B on cathode current collector 53A 53。

In this case, first, by lithium carbonate (Li₂CO₃) and cobalt carbonate (CoCO₃) mixed in molar ratio with 0.5: 1.It After, mixture is fired 5 hours in atmosphere at 900 DEG C.Thus, it is thus achieved that lithium cobalt composite oxide (LiCoO₂).Subsequently, will 91 mass parts as the lithium cobalt composite oxide of active material of cathode, the graphite as negative electrode conductive agent of 6 mass parts and 3 matter The Kynoar as cathode adhesive of amount part carries out mixing to obtain cathode mix.Subsequently, by this cathode mix It is dispersed in METHYLPYRROLIDONE to obtain pasty state cathode mixture slurry.Subsequently, uniform with this cathode mixture slurry Two faces of ground coated cathode collector 53A, are dried thus form cathode active material 53B.As cathode current collector 53A, uses band-shaped aluminium foil (thickness: 12 μm).Finally, by using roll squeezer to be compressed into by cathode active material 53B Type.

Then, by using spraying method (gas flame spraying method) to form anode activity in anode collector 54A Material layer 54B and form anode 54.

In this case, by towards two face spraying molten states of anode collector 54A or semi-molten state Si powder (median size: 1 μm-300 μm, including two end values) formation as anode material comprises multiple active material of positive electrode Anode active material layers 54B of granule.As anode collector 54A, use roughened electrolytic copper foil (thickness: 18 μm, ten Point mean roughness Rz:4 μm).By setting spheroidal particle and the presence or absence of aspherical particle shown in table 1.In spraying process, make By the mixed gas of hydrogen and oxygen (hydrogen: oxygen=2: 1, volume ratio) as spray gas, use nitrogen as material supply gas, and And spray rate is about 45m/s-about 55m/s (including two end values).In this case, by regulation material supply gas amount Control the material input quantity of time per unit.It addition, for preventing anode collector 54A hot injury, carry out the same of spray treatment Time use carbon dioxide cool down.Especially, introduce oxygen in room, thus the oxygen in anode active material particles is contained Amount is set as 5 atom %.

In forming anode active material layers 54B, by the regulation median size of anode material, input quantity and fusion temperature And the chilling temperature of base material, meet following condition.First, aspherical particle comprises flat particle.Secondly, X-ray is passed through The half-peak breadth (2 θ) of the diffraction maximum in (111) crystal face of the anode active material particles that diffraction obtains is 1 degree, and comes from this crystalline substance The crystallite dimension in face is 40nm.In this case, employ Rigaku company manufacture X-ray diffraction device (pipe: CuK α), X-ray tube voltage is 40kV, and x-ray tube current is 40mA, and scan method is θ-2 θ method, and measurement scope is 20 degree≤2 θ≤90 Degree.3rd, by setting the presence or absence of spheroidal particle, its number, its particle diameter (median size) and its circularity shown in table 1.For Above-mentioned condition, checks the non-relative region R2 with reference to anode active material layers 54B shown in Fig. 9.Calculate the particle diameter of spheroidal particle And number object program is with regard to as described in aforesaid anode.

Then, mixed carbonic acid ethyl (EC) and diethyl carbonate (DEC) are as solvent.Afterwards, will be as electrolytic salt Lithium hexafluoro phosphate (LiPF₆) be dissolved in solvent to prepare liquid electrolyte (electrolyte).In this case, solvent composition (EC: DEC) is 50: 50 weight ratios.Electrolytic salt is 1mol/kg relative to the content of solvent.

Finally, by using negative electrode 53, anode 54 and electrolyte to carry out secondary cell for assembling.First, by the moon made of aluminum Pole lead-in wire 51 is soldered to one end of cathode current collector 53A, and the anode tap 52 being made up of nickel is soldered to anode collector 54A One end.Subsequently, negative electrode 53, spacer body 55, anode 54 and spacer body 55 with this order stacking and are wound along longitudinal spiral.It After, protected with 57 end sections fixing this screw winding body by be made up of adhesive tape, thus formed as screw winding The screw winding body of the precursor of electrode body 50.As spacer body 55, use three-decker (thickness: 23 μm), in this structure, by micro- Hole polyethylene is clipped between the film being made up as key component of capillary polypropylene as the film that key component is made.Subsequently, will This screw winding body is clipped between packaging part 60.Afterwards, the outer edge in addition to the edge of packaging part side is carried out heat each other Fusion.Thus screw winding body is contained in bag-shaped packaging part 60.As packaging part 60, use 3 layers of laminate film (total thickness Degree: 100 μm), in this film, stacking nylon membrane (thickness: 30 μm), aluminium foil (thickness: 40 μm) and cast polypropylene film from outside (thickness: 30 μm).Subsequently, inject electrolyte by the opening of packaging part 60, make electrolysis immersion be contained in spacer body 55, thus shape Become spiral winding electrode 50.Finally, by heat fused, the opening of packaging part 60 is sealed in vacuum atmosphere, thus, complete Lamination membranous type secondary cell.In forming secondary cell, by regulating the thickness of cathode active material 53B, prevent lithium gold Belong to and being deposited on the anode 54 of fully charged state.

Check cycle characteristics and the expansion characteristics of the secondary cell of embodiment 1-1 to 1-10.Obtain institute in table 1 and Figure 14 The result shown.

In checking cycle characteristics, it is circulated test, thus obtains discharge capacitance.First, for stable cell State, after carrying out 1 charging and discharging circulation, again charges and discharges and follows at second to measure in the atmosphere of 23 DEG C Discharge capacity during ring.Subsequently, by this secondary cell charging and discharging 99 circulation in identical atmosphere, thus the 101st Discharge capacity is measured during individual circulation.Finally, calculating discharge capacitance (%)=(discharge capacity when the 101st circulation/ Discharge capacity when the 2nd circulation) * 100.In this case, with 3mA/cm²Constant current density be charged until After cell voltage reaches 4.2V, proceed charging with the constant voltage of 4.2V until cell density reaches 0.3mA/cm².Further Ground, with 3mA/cm²Constant current density carry out electric discharge until cell voltage reach 2.5V.

In checking expansion characteristics, obtain expansion rate when aforementioned loop test.That is, the electric discharge the 2nd circulation is measured After thickness and the 101st circulation electric discharge after thickness.Afterwards, calculating expansion rate (%)=[(the 101st circulation Thickness after electric discharge-the 2nd circulation electric discharge after thickness)/the 2nd circulation electric discharge after thickness] * 100.

Check that cycle characteristics and the program of expansion characteristics and condition are similarly applicable for the following examples.

Table 1

Battery structure: lamination membranous type；Active material of cathode: LiCoO₂；Active material of positive electrode: Si (spraying process)；Anode collection 10 mean roughness Rz:4 μm of fluid；Oxygen content in anode active material particles: 5 atom %

In multiple anode active material particles comprise the embodiment 1-1 to 1-9 of spheroidal particle, with multiple anode activity materials It is visibly different that material granule does not comprise embodiment 1-10 of spheroidal particle, and discharge capacitance brings up to about 80% or more Greatly, and expansion rate is reduced to about 1% or less.Especially, the feelings of spheroidal particle are comprised at multiple anode active material particles In shape, the trend existed is, along with particle diameter increases, discharge capacitance improves and then reduces, and expansion rate reduces.? In this situation, when being 0.5 μm-35 μm (including two end values) for particle diameter, more improve discharge capacitance, more Add reduction expansion rate, and obtain enough battery capacities.Therefore, spheroidal particle is comprised at multiple anode active material particles In situation, it is thus achieved that excellent cycle characteristics and excellent expansion rate.In this case, for spheroidal particle particle diameter (in Value size) it is the situation of 0.5 μm-35 μm (including two end values), the two characteristic is further improved.

Embodiment 2-1 to 2-8

Performing similarly to the operation of embodiment 1-5, difference is by the circle changing spheroidal particle shown in table 2 Degree.Check cycle characteristics and the expansion characteristics of the secondary cell of embodiment 2-1 to 2-8.Obtain the knot shown in table 2 and Figure 15 Really.

Table 2

Battery structure: lamination membranous type；Active material of cathode: LiCoO₂；Active material of positive electrode: Si (spraying process), anode collection 10 mean roughness Rz:4 μm of fluid；Oxygen content in anode active material particles: 5 atom %

In multiple anode active material particles comprise the embodiment 2-1 to 2-8 of spheroidal particle, with multiple anode activity materials Embodiment 1-10 that material granule does not comprise spheroidal particle is visibly different, even when changing circularity, it is thus achieved that The discharge capacitance of about 80% or bigger and the expansion rate of about 1% or less.Especially, at multiple active material of positive electrode Grain comprises in the situation of spheroidal particle, and the trend existed is, along with circularity reduces, discharge capacitance improves and expansion rate Reduce.In this case, when being 0.5-1 (including two end values) for circularity, more improve discharge capacity and keep Rate, more reduces expansion rate, and obtains enough battery capacities.Therefore, circularity is that 0.5-1 (includes two ends wherein Value) situation in, the two characteristic is further improved.

Embodiment 3-1 to 3-11

Performing similarly to the operation of embodiment 1-4, difference is by the number changing spheroidal particle shown in table 3. Check cycle characteristics and the expansion characteristics of the secondary cell of embodiment 3-1 to 3-11.Obtain the knot shown in table 3 and Figure 16 Really.

Table 3

Battery structure: lamination membranous type；Active material of cathode: LiCoO₂；Active material of positive electrode: Si (spraying process)；Anode collection 10 mean roughness Rz:4 μm of fluid；Oxygen content in anode active material particles: 5 atom %

In multiple anode active material particles comprise the embodiment 3-1 to 3-11 of spheroidal particle, with multiple anodes activity Embodiment 1-10 that material granule does not comprise spheroidal particle is visibly different, even when changing numbers of particles, obtains Obtained discharge capacitance and the expansion rate of about 1% or less of about 80% or bigger.Especially, at multiple anode activity materials Material granule comprises in the situation of spheroidal particle, and the trend existed is, along with numbers of particles increases, discharge capacitance improve and Expansion rate reduces.In this case, when being 10pcs-200pcs (including two end values) for numbers of particles, more carry High discharge capacitance, more reduces expansion rate, and obtains enough battery capacities.Therefore, at numbers of particles it is In the situation of 10pcs-200pcs (including two end values), the two characteristic is further improved.

Embodiment 4-1 to 4-5

Performing similarly to the operation of embodiment 1-5, difference is by changing half-peak breadth and crystallite chi shown in table 4 Very little.Check cycle characteristics and the expansion characteristics of the secondary cell of embodiment 4-1 to 4-5.Obtain the knot shown in table 4 and Figure 17 Really.

Table 4

Battery structure: lamination membranous type；Active material of cathode: LiCoO₂；Active material of positive electrode: Si (spraying process)；Anode collection 10 mean roughness Rz:4 μm of fluid；Oxygen content in anode active material particles: 5 atom %

During anode active material particles is the embodiment 4-1 to 4-5 of crystalline state wherein, the trend existed is, along with half-peak Wide increasing reduces with crystallite dimension, and expansion rate is constant simultaneously, and discharge capacitance reduces.In this case, for half-peak A width of 20 degree or less and situation that crystallite dimension is 10nm or bigger, more improve discharge capacitance.Therefore, at sun Pole active material particle is in the situation of crystalline state, it is thus achieved that excellent cycle characteristics.In this case, for passing through X-ray The half-peak of diffraction maximum in (111) crystal face of the active material of positive electrode that diffraction obtains a width of 20 degree or less and crystallite dimension are The situation of 10nm or bigger, more improves cycle characteristics.

Embodiment 5-1 to 5-4

Performing similarly to the operation of embodiment 1-1 to 1-10, difference is to form anode activity material by cladding process Bed of material 54B.In forming anode active material layers 54B, first, the spheroidal particle being made up of Si powder and aspherical are prepared Grain.In this case, Si powder melted and the most at once cool down to obtain spheroidal particle.Meanwhile, Si powder is melted also Then use cooling gas (nitrogen) appropriateness cooling to obtain aspherical particle.Subsequently, using aforementioned as active material of positive electrode Si powder (described spheroidal particle and aspherical particle) and for forming the polyamic acid solution (solvent: N-first of anode binder Base-2-Pyrrolidone and N,N-dimethylacetamide) mix with the dry weight ratio of 80: 20 to obtain anode mixture.Subsequently, will This anode mixture is dispersed in METHYLPYRROLIDONE to obtain pasty state anode mixture slurry.Subsequently, it is coated with by use Coating device two faces of this anode mixture slurry uniform coated anode collector 54A and dry gains.Finally, very Air atmosphere provides heat treatment to gains under conditions of 400 DEG C and continues 1 hour to form anode active material layers 54B.Illustrate the presence or absence of spheroidal particle in this situation, its number, its particle diameter and circularity thereof in table 5.Check embodiment The cycle characteristics of the secondary cell of 5-1 to 5-4 and expansion characteristics.Obtain the result shown in table 5.

Table 5

Battery structure: lamination membranous type；Active material of cathode: LiCoO₂；Active material of positive electrode: Si (spraying process)；Anode collection 10 mean roughness Rz:4 μm of fluid；Oxygen content in anode active material particles: 5 atom %

Use wherein cladding process as in the embodiment 5-1 to 5-4 of the forming method of anode active material layers 54B, phase Comparing in the embodiment 1-1 to 1-10 wherein using spraying process, discharge capacitance reduces and expansion rate improves.Result shows Show, if using cladding process, unlike use spraying process, it is impossible to enough form wherein spheroidal particle and mix mutually with aspherical particle The ideal system closed, and expansion and the contraction of anode active material layers 54B is the most sufficiently prevented when charging and discharging.Cause This, in the situation that anode active material layers 54B is formed by spraying process, it is possible to form wherein spheroidal particle and aspherical particle The ideal system mixed mutually, and therefore obtain the cycle characteristics of excellence.

Embodiment 6-1 to 6-3

Performing similarly to the operation of embodiment 1-5,1-6 and 1-10, it is flat that difference is that aspherical particle does not comprise Granule.Check cycle characteristics and the expansion characteristics of the secondary cell of embodiment 6-1 to 6-3.Obtain the result shown in table 6.

Table 6

Battery structure: lamination membranous type；Active material of cathode: LiCoO₂；Active material of positive electrode: Si (spraying process)；Anode collection 10 mean roughness Rz:4 μm of fluid；Oxygen content in anode active material particles: 5 atom %

In multiple anode active material particles comprise embodiment 6-1 and the 6-2 of spheroidal particle, live compared to multiple anodes Property material granule does not comprise embodiment 6-3 of spheroidal particle, even if in aspherical particle does not comprise the situation of flat particle, puts Capacitance conservation rate brings up to about 70% or bigger, and expansion rate is reduced to about 1% or less.Especially, with wherein aspherical Grain does not comprise the situation of flat particle and compares, and in aspherical particle comprises the situation of flat particle, discharge capacitance carries High and expansion rate reduces.Therefore, in aspherical particle comprises the situation of flat particle, further improve cycle characteristics and Expansion characteristics.

Embodiment 7-1 to 7-9

Performing similarly to the operation of embodiment 1-5, difference is by changing anode active material particles shown in table 7 Oxygen content.Check cycle characteristics and the expansion characteristics of the secondary cell of embodiment 7-1 to 7-9.Obtain institute in table 7 and Figure 18 The result shown.

Table 7

Battery structure: lamination membranous type；Active material of cathode: LiCoO₂；Active material of positive electrode: Si (spraying process)；Anode collection 10 mean roughness Rz:4 μm of fluid

In multiple anode active material particles comprise the embodiment 7-1 to 7-9 of spheroidal particle, with multiple anode activity materials Material granule does not comprise embodiment 1-10 of spheroidal particle and compares, even if when changing oxygen content, also obtain about 80% or bigger Discharge capacitance and the expansion rate of about 1% or less.Especially, spherical is comprised at multiple anode active material particles In the situation of grain, the trend existed is, along with oxygen content increases, discharge capacitance raising and simultaneously expansion rate are constant.? In this situation, when oxygen content is 1.5 atom %-40 atom % (including two end values), discharge capacitance more carries Height, expansion rate more reduces, and obtains enough battery capacities.Therefore, the oxygen content in anode active material particles is 1.5 in the situation of atom %-40 atom % (including two end values), further improve cycle characteristics.

Embodiment 8-1 to 8-16

Performing similarly to the operation of embodiment 1-5, difference is that active material of positive electrode has shown in table 8 and table 9 Metallic element.For this situation, by by every kind of metal together with silicon in formation of deposits anode active material layers 54B, Metal element content in anode active material particles is set as 5 atom %.Check the secondary cell of embodiment 8-1 to 8-16 Cycle characteristics and expansion characteristics.Obtain the result shown in table 8 and table 9.

In multiple anode active material particles comprise the embodiment 8-1 to 8-16 of spheroidal particle, with multiple anodes activity Material granule does not comprise embodiment 1-10 of spheroidal particle and compares, and even has the feelings of metallic element at anode active material particles In shape, it is thus achieved that the discharge capacitance of about 80% or bigger and the expansion rate of about 1% or less.Especially, live at anode Property material have in the situation of metallic element, discharge capacitance does not have metal unit higher than wherein anode active material particles The discharge capacitance of the situation of element, expansion rate does not have the feelings of metallic element equal to wherein anode active material particles simultaneously The expansion rate of shape.Therefore, in anode active material particles has the situation of metallic element, cycle characteristics is changed further Kind.

Embodiment 9-1 to 9-3

Performing similarly to the operation of embodiment 1-5, difference is that forming anode active material layers 54B makes high oxygen-containing Region is clipped between low oxygen-containing region, and high oxygen-containing region and low oxygen-containing region alternately laminated.In this case, by table 10 Shown in the number in high oxygen-containing region is set.Check cycle characteristics and the expansion characteristics of the secondary cell of embodiment 9-1 to 9-3. Obtain the result shown in table 10 and Figure 19.

In multiple anode active material particles comprise the embodiment 9-1 to 9-3 of spheroidal particle, with multiple anode activity materials Material granule does not comprise embodiment 1-10 of spheroidal particle and compares, even anode active material layers 54B have high oxygen-containing region and In the situation in low oxygen-containing region, it is thus achieved that the discharge capacitance of about 80% or bigger and the expansion rate of about 1% or less.Special Not, in anode active material layers 54B has the situation in high oxygen-containing region and low oxygen-containing region, with wherein active material of positive electrode Layer 54B does not have high oxygen-containing region and compares with the situation in low oxygen-containing region, and discharge capacitance improves and expansion rate reduces. In this case, along with the number in the high oxygen-containing region of increase, discharge capacitance improves and expansion rate reduces.Therefore exist Anode active material layers 54B has in the situation in high oxygen-containing region and low oxygen-containing region, and cycle characteristics and expansion characteristics are entered One step is improved.

Embodiment 10-1 to 10-13

Performing similarly to the operation of embodiment 1-5, difference is that 10 of the surface of anode collector 54A are average thick Rugosity Rz is changed shown in table 11.Check the cycle characteristics of the secondary cell of embodiment 10-1 to 10-13 and expand spy Property.Obtain the result shown in table 11 and Figure 20.

In multiple anode active material particles comprise the embodiment 10-1 to 10-13 of spheroidal particle, live with multiple anodes Property material granule do not comprise embodiment 1-10 of spheroidal particle and compare, even in the situation changing 10 mean roughness Rz, Obtain discharge capacitance and the expansion rate of about 1% or less of about 70% or bigger.Especially, in multiple anodes activity Material granule comprises in the situation of spheroidal particle, and the trend existed is, along with improving 10 mean roughness Rz, discharge capacity is protected Holdup improves and then reduces and expansion rate is constant simultaneously.In this case, it is 1.5 μm for 10 mean roughness Rz Or the bigger or situation of preferably 3 μm-30 μm (including two end values), discharge capacitance more improves, and obtains enough Battery capacity.Therefore, 10 mean roughness Rz for the surface of anode collector 2A are 1.5 μm or bigger or preferably 3 The situation of μm-30 μm (including two end values), cycle characteristics is further improved.

Embodiment 11-1 to 11-8

Performing similarly to the operation of embodiment 1-5, difference is that the composition of electrolyte is by shown in table 12 and table 13 It is changed.In this case, as solvent, the 4-as the cyclic carbonate with halogen fluoro-1 shown in use formula 2, 3-dioxole-2-ketone (FEC), or shown in formula 2 as 4 of the cyclic carbonate with halogen, 5-bis-fluoro-1, 3-dioxolan-2-one (DFEC).It addition, as other solvent, as having the ring-type of unsaturated carbon bond shown in use formula 3 The vinylene carbonate (VC) of carbonic ester, or the ethylene as the cyclic carbonate with unsaturated carbon bond shown in formula 4 Thiazolinyl ethyl (VEC).It addition, as electrolytic salt, use LiBF4 (LiBF₄).Additionally, as other solvent, make With propene sultone (PRS) as sultone.It addition, use sulfosalicylic acid acid anhydride (SBAH) as anhydride or Sulfo propionic acid acid anhydride (SPAH) as anhydride.In this case, in solvent, the content of other solvent is 1 weight %.Check embodiment 11-1 to 11- The cycle characteristics of the secondary cell of 8 and expansion characteristics.Obtain the result shown in table 12 and table 13.

Table 12

Battery structure: lamination membranous type；Active material of cathode: LiCoO₂；Active material of positive electrode: Si (spraying process)；Anode collection 10 mean roughness Rz:4 μm of fluid, the oxygen content in anode active material particles: 5 atom %

Table 13

Battery structure: lamination membranous type；Active material of cathode: LiCoO₂；Active material of positive electrode: Si (spraying process)；Anode collection 10 mean roughness Rz:4 μm of fluid；Oxygen content in anode active material particles: 5 atom %

Addition FEC etc. as solvent and add other solvent and the LiBF as electrolytic salt wherein₄Embodiment In 11-1 to 11-8, compared to being wherein added without FEC etc. and LiBF₄Embodiment 1-5, electric discharge conservation rate improve, expand simultaneously Rate is equal with embodiment 1-5.It addition, add in the embodiment 11-6 to 11-8 of PRS etc. wherein, compared to being wherein not added with Entering embodiment 1-5 of PRS etc., expansion rate reduces.Therefore, for use have the linear carbonate of halogen or cyclic carbonate, Having the cyclic carbonate of unsaturated carbon bond, sultone or the anhydride situation as solvent, cycle characteristics is improved.It addition, Using LiBF4 as in the situation of electrolytic salt, cycle characteristics is further improved.It addition, using sultone With anhydride as in the situation of solvent, expansion characteristics is improved.

Embodiment 12-1 to 12-4

Performing similarly to the operation of embodiment 1-5, difference is the lithium nickel composite oxide shown in use table 14 As active material of cathode.In this case, as lithium nickel composite oxide, use LiNi_0.70Co_0.25Al_0.05O₂、 LiNi_0.79Co_0.14Mn_0.07O₂、LiNi_0.70Co_0.25Mg_0.05O₂, or LiNi_0.70Co_0.25Fe_0.05O₂.Check embodiment 12-1 to 12- The cycle characteristics of the secondary cell of 4 and expansion characteristics.Obtain the result shown in table 14.

Use lithium/nickel/cobalt composite oxide as in the embodiment 12-1 to 12-4 of active material of cathode wherein, expanding While the rate expansion rate equal to wherein embodiment 1-5 of use lithium cobalt composite oxide, discharge capacitance is compared to reality Execute example 1-5 to be improved.Therefore, use lithium/nickel/cobalt composite oxide as in the situation of active material of cathode, cycle characteristics It is further improved.

Embodiment 13-1 to 13-2

Performing similarly to the operation of embodiment 1-5, difference is to manufacture rectangular secondary cell.Manufacture this square two In primary cell, first, negative electrode 21 and anode 22 are formed.Afterwards, the cathode leg 24 made by aluminum is soldered to cathode current collector 21A, the anode tap 25 made by nickel is soldered to anode collector 22A.Subsequently, by negative electrode 21, spacer body 23 and anode 22 with This order stacking also winds along longitudinal spiral.Afterwards, the lamilated body of screw winding is configured to flat to form cell device 20.Subsequently, cell device 20 is contained in the battery case 11 being made up of the material shown in table 15.Afterwards, by insulation board 12 It is arranged on cell device 20.Subsequently, cathode leg 24 is soldered to negative electrode pin 15, and anode tap 25 is soldered to battery case 11.Afterwards, battery cover 13 is laser welded to the opening of battery case 11.Finally, electrolyte is being injected electricity by hand-hole 19 After pond shell 11, seal this hand-hole 19 by sealing member 19A.Thus complete rectangular cell.Check embodiment 13-1 and 13-2 The cycle characteristics of secondary cell and expansion characteristics.Obtain the result shown in table 15.

During battery structure is embodiment 13-1 of square and 13-2 wherein, with the reality that wherein battery structure is lamination membranous type Executing example 1-5 to compare, discharge capacitance improves and expansion rate reduces.Especially, battery case 11 is fabricated from iron wherein In square, discharge capacitance obtains bigger raising and expansion rate obtains bigger reduction.Therefore, for the battery structure side of being The situation of type, cycle characteristics and expansion characteristics are further improved.

Embodiment 14-1 to 14-18

Performing similarly to the operation of embodiment 8-1, difference is, as shown in table 16 and table 17, changes anode and lives The composition (crystallite dimension and metal element content) of property material granule and form metal level.Forming active material of positive electrode 54B In, repeated several times forms multiple anode active material particles and then by using electrolytic plating method shape by using spraying process Become the step of metal level.In this case, the ferrum plating solution conduct that use Japan Pure Chemical Co., Ltd. manufactures Plating solution, electric current density is 2A/dm²-5A/dm²(including two end values), plating rate is 5nm/s.It addition, the concentration of regulation plating solution With Plating times to change the thickness of metal level.Check the cycle characteristics of the secondary cell of embodiment 14-1 to 14-8.Obtain Result shown in table 16 and table 17.

Formed in the embodiment 14-1 to 14-17 of metal level wherein, with embodiment 14-without formation metal level 8 compare, and discharge capacitance improves.Such result shows, in the situation forming metal level, and anode active material particles Metal level between with is combined, and metal level protection electrolyte affects from active material of positive electrode.Especially, the trend existed is, Along with metal layer thickness increases, discharge capacitance improves.In this case, it is that 1nm-30000nm (includes for thickness Two end values) situation, discharge capacitance improve and obtain enough battery capacities.Therefore, metal level is being formed Situation in, cycle characteristics is further improved.It addition, be that 1nm-30000nm (includes two ends for metal layer thickness Value) situation, it is thus achieved that excellent battery capacity and excellent cycle characteristics.

Embodiment 15-1 to 15-19

Performing similarly to the operation of embodiment 14-1 to 14-17, difference is to change by shown in table 18 and table 19 The formation material of metal level and thickness.Formed in metal level, using Japan Pure Chemical Co., Ltd. to manufacture Copper electrolyte, nickel plating bath, cobalt plating solution, zinc plating solution and chromium plating solution are as plating solution, and plating rate is 5nm/s.It addition, electric current density As follows: to be 2A/dm in copper electrolyte²-8A/dm²(including two end values), is 2A/dm in nickel plating bath²-10A/dm²(include two Individual end value), it is 1A/dm in cobalt plating solution²-8A/dm²(including two end values), is 1A/dm in zinc plating solution²-3A/dm²(include Two end values), and be 2A/dm in chromium plating solution²-6A/dm²(including two end values).Check the two of embodiment 15-1 to 15-19 The cycle characteristics of primary cell.Obtain the result shown in table 18 and table 19.

Wherein change metal level formed material embodiment 15-1 to 15-19 in, with without formed metal level Embodiment 14-18 compare, discharge capacitance is higher.Therefore, when material is formed for change metal level, circulation Characteristic is further improved.

Embodiment 16-1 to 16-25

Performing similarly to the operation of embodiment 14-7, difference is in anode active material particles not contain ferrum, or Person presses and changes the iron content in anode active material particles shown in table 20 and 21 or change the gold in anode active material particles Belong to element type.Check the cycle characteristics of the secondary cell of embodiment 16-1 to 16-25.Obtain shown in table 20 and table 21 Result.

Change the embodiment 16-1 to 16-25 of the metallic element composition comprised in anode active material particles wherein In, compared with embodiment 14-18 without formation metal level, discharge capacitance is higher.Therefore, even if changing sun In the situation of the composition of the metallic element comprised in the active material of pole, cycle characteristics is further improved.

Embodiment 17-1 to 17-13

Performing similarly to the operation of embodiment 14-7, difference is by changing half-peak breadth and crystallite chi shown in table 22 Very little.Check the cycle characteristics of the secondary cell of embodiment 17-1 to 17-13.Obtain the result shown in table 22.

It is formed therein in the embodiment 17-1 to 17-13 of metal level, 20 degree or less and crystallite a width of for half-peak The situation of a size of 10nm or bigger, discharge capacitance more improves.Therefore, even the situation of metal level is being defined In, if in (111) crystal face of the anode active material particles obtained by X-ray diffraction the half-peak of diffraction maximum a width of 20 degree or Less and that crystallite dimension is 10nm or bigger situation, cycle characteristics is further improved.

Embodiment 18-1 to 18-3

Performing similarly to the operation of embodiment 14-6,14-7 and 14-9, it is flat that difference is that aspherical particle does not comprise Flat granule.Check the cycle characteristics of the secondary cell of embodiment 18-1 to 18-3.Obtain the result shown in table 23.

During aspherical particle does not comprise the embodiment 18-1 to 18-3 of flat particle wherein, and wherein do not form metal level Embodiment 14-18 compare, discharge capacitance is higher.Therefore, even in the situation defining metal level, if aspheric Shape granule comprises flat particle, then cycle characteristics is further improved.

Embodiment 19-1 to 19-9

Performing similarly to the operation of embodiment 14-7, difference is by changing active material of positive electrode shown in table 24 Oxygen content in Li.Check cycle characteristics and the expansion characteristics of the secondary cell of embodiment 19-1 to 19-9.Obtain in table 24 Shown result.

Formed in the embodiment 19-1 to 19-9 of metal level wherein, even in the situation changing oxygen content, and wherein Embodiment 14-18 not forming metal level is compared, and discharge capacitance is higher.In this case, it is 1.5 for oxygen content The situation of atom %-40 atom % (including the situation of two end values), discharge capacitance more improves, and obtains foot Enough battery capacities.Therefore, in the situation forming metal level, if the oxygen content in anode material granule is 1.5 atom %- 40 atom % (include two end values), then cycle characteristics is further improved.

Embodiment 20-1 to 20-3

Performing similarly to the operation of embodiment 14-7, difference is to comprise high oxygen-containing region by formation shown in table 25 Anode active material layers 54B with low oxygen-containing region.Check the cycle characteristics of the secondary cell of embodiment 20-1 to 20-3.Obtain Result shown in table 25.

Formed wherein in the embodiment 20-1 to 20-3 of metal level, even comprise height in anode active material layers 54B and contain In the situation in oxygen region and low oxygen-containing region, compared with embodiment 14-18 wherein not forming metal level, discharge capacitance Higher.Therefore, even in the situation forming metal level, if anode active material layers 54B has high oxygen-containing region and low contains Oxygen region, then cycle characteristics is further improved.

Embodiment 21-1 to 21-12

Performing similarly to the operation of embodiment 14-7, difference is by changing anode collector 54A shown in table 26 10 mean roughness Rz on surface.Check the cycle characteristics of the secondary cell of embodiment 21-1 to 21-12.Obtain in table 26 Shown result.

Formed in the embodiment 21-1 to 21-12 of metal level wherein, even in the feelings changing 10 mean roughness Rz In shape, compared with embodiment 14-8 wherein not forming metal level, discharge capacitance is higher.In this case, for 10 mean roughness Rz be 1.5 μm or more greatly, the situation of preferably 3 μm-30 μm (including two end values), discharge capacitance More improve.Therefore, even in the situation forming metal level, if the ten of anode collector 54A mean roughness Rz are 1.5 μm or more greatly, preferably 3 μm-30 μm (including two end values), then cycle characteristics is further improved.

Embodiment 22-1 to 22-8

Performing similarly to the operation of embodiment 14-7, difference is by changing electrolyte shown in table 27 and table 28 Composition.The particular make-up of electrolyte is similar to those in embodiment 11-1 to 11-8.Check the two of embodiment 22-1 to 22-8 The cycle characteristics of primary cell.Obtain the result shown in table 27 and table 28.

Table 28

Battery structure: lamination membranous type；Active material of cathode: LiCoO₂；Active material of positive electrode: Si (spraying process)；Anode collection 10 mean roughness Rz:5 μm of fluid；Oxygen content in anode active material particles: 5 atom %

Formed in the embodiment 22-1 to 22-8 of metal level wherein, even in changing the situation of composition of electrolyte, Compared with embodiment 14-18 not forming metal level, discharge capacitance is higher.Therefore, even in the feelings forming metal level In shape, if using linear carbonate or the cyclic carbonate with halogen, there is the cyclic carbonate of unsaturated carbon bond, in sulphur Ester, or anhydride, then cycle characteristics is further improved.It addition, using the LiBF4 situation as electrolytic salt In, cycle characteristics is further improved.It addition, using sultone or anhydride as in the situation of solvent, cycle characteristics obtains To improving further.

Embodiment 23-1 to 23-2

Performing similarly to the operation of embodiment 14-7, difference is by manufacturing rectangular secondary cell shown in table 29. The operation of embodiment 13-1 and 13-2 it is similar to for manufacturing the operation of square secondary cell.Check embodiment 23-1 and 23-2 The cycle characteristics of secondary cell.Obtain the result shown in table 29.

Formed in the embodiment 23-1 to 23-2 of metal level wherein, even in the situation changing battery structure, and not Embodiment 14-18 forming metal level is compared, and discharge capacitance is higher.In this case, for the battery structure side of being The situation of shape, discharge capacitance more improves.Therefore, even in the situation forming metal level, if battery structure is Square, cycle characteristics is further improved.

By the result of table 1 to table 29 and Figure 14 to Figure 20, confirm as follows.That is, the anode in the secondary cell of the present invention is lived Property material layer comprises and multiple has the silicon crystalline state anode active material particles as constituent element.The plurality of crystalline state active material of positive electrode Grain comprises spheroidal particle and aspherical particle.It is thus achieved that the cycle characteristics of excellence and excellent expansion characteristics and be not dependent on With or without metallic element, electrolyte composition, battery knot in oxygen content in anode active material particles, anode active material particles Structure, the presence or absence etc. of metal level.

The present invention is described with reference to embodiment and embodiment.But, the present invention is not limited in foregoing embodiments With the aspect described in previous embodiment, but may be made that various amendment.Such as, the use of the anode of the present invention is not Always it is limited to secondary cell, and can be the electrochemical appliance beyond secondary cell.The example of other use includes electricity Container.

It addition, in foregoing embodiments and previous embodiment, given the description of lithium rechargeable battery as it Anodic capacity is based on the secondary cell type embedded and abjection lithium ion represents.But, the secondary cell of the present invention is not It is limited to this.The present invention can be applied similarly to following secondary cell: wherein anode capacity includes and embeds and abjection lithium ion Relevant capacity and with the precipitation of lithium metal and dissolve relevant capacity, and anode capacity is by the summation table of these capacity Show.In this case, use and can embed and deviate from the material of lithium ion as active material of positive electrode, and such material In chargeable capacity be set as value less compared with the discharge capacity of negative electrode.

It addition, in foregoing embodiments and previous embodiment, it has been described that wherein battery structure be square, column type or The instantiation of the situation of lamination membranous type, and wherein cell device has the instantiation of spiral wound arrangements.But, this Bright secondary cell can be applied similarly to the battery with other battery structure, such as Coin-shaped battery and button type electricity Pond, or wherein cell device has the battery of other structure such as laminate structures.

It addition, in foregoing embodiments and previous embodiment, it has been described that use lithium as the situation of electrode reaction thing, But electrode reaction thing is not limited to this.But, such as can use other 1 race element such as sodium (Na) and potassium (K), 2 race's element such as magnesium With calcium or other light metal such as aluminum as electrode reaction thing.It is obtained in that the effect of the present invention is not dependent on reacting species Type, even and if therefore change electrode reaction species type, it is also possible to obtain similar effect.

It addition, in foregoing embodiments and previous embodiment, for the particle diameter of the spheroidal particle of secondary cell of the present invention, Provide the description of the proper range derived by embodiment result.But, this description not exclusively denies that particle diameter is outside aforementioned range Probability.That is, aforementioned proper range is to obtain the particularly preferred scope of the effect of the present invention.Therefore, as long as obtaining The effect of the present invention, particle diameter can deviate aforementioned range in some degree.This is equally applicable to the circularity of spheroidal particle, sun Oxygen content in the half-peak breadth of pole active material particle and crystallite dimension, anode active material particles, anode current collector surface 10 mean roughness Rz or the thickness of metal level.

The Japanese Priority Patent application that the theme that the application comprises relates on November 14th, 2008 to be submitted in Japan Office The Japanese Priority Patent application JP2009-150923's that JP2008-291850 and on June 15th, 2009 submit in Japan Office Theme, entire contents is incorporated herein by.

It will be understood by those of skill in the art that and require and other factors according to design, various amendment, group can be carried out Conjunction, secondary combination and change, as long as they are in the range of appended claims or its equivalents.

Claims (19)

1. secondary cell, comprises:

Can embed and deviate from negative electrode and the anode of electrode reaction thing；With

Containing solvent and the electrolyte of electrolytic salt, its Anodic has anode active material layers in anode collector,

Containing multiple there is the silicon (Si) anode active material layers as the crystalline state anode active material particles of constituent element, and

The plurality of anode active material particles contains spheroidal particle and aspherical particle, wherein the median size grain of spheroidal particle Footpath is 0.1 μm-40 μm, including two end values；And wherein the circularity of spheroidal particle is 0.5-1, including two end values.

Secondary cell the most according to claim 1, (111) of the anode active material particles wherein obtained by X-ray diffraction Diffraction maximum half-peak breadth (2 θ) in crystal face is 20 degree or less, or the anode active material particles obtained by X-ray diffraction The crystallite dimension coming from (111) crystal face be 10nm or bigger.

Secondary cell the most according to claim 1, wherein the median size particle diameter of spheroidal particle is 0.5 μm-35 μm, including two End value.

Secondary cell the most according to claim 1, at least a part of which part aspherical particle is flat.

Secondary cell the most according to claim 1, wherein anode active material particles is formed by spraying process.

Secondary cell the most according to claim 1, wherein anode active material particles and anode collector are at least part of interface Place's alloying.

Secondary cell the most according to claim 1, during wherein anode active material particles is the simple substance of silicon, alloy and compound At least one.

Secondary cell the most according to claim 1, wherein anode active material particles has oxygen (O) as constituent element, and this sun Oxygen content in the active material particle of pole is 1.5 atom %-40 atom %, including two end values.

Secondary cell the most according to claim 1, wherein anode active material particles have following at least one metal unit Element is as constituent element: ferrum (Fe), nickel (Ni), molybdenum (Mo), titanium (Ti), chromium (Cr), cobalt (Co), copper (Cu), manganese (Mn), zinc (Zn), germanium (Ge), aluminum (Al), zirconium (Zr), silver (Ag), stannum (Sn), antimony (Sb) and tungsten (W).

Secondary cell the most according to claim 8, wherein anode active material layers comprises, at thickness direction, the height that oxygen content is higher Oxygen-containing region and the relatively low low oxygen-containing region of oxygen content.

11. secondary cells according to claim 1, wherein 10 mean roughness Rz of anode current collector surface be 1.5 μm or Bigger.

12. secondary cell according to claim 1, wherein solvent contains one of the following or multiple: have halogen shown in formula 1 Element is as having halogen as the tool shown in the cyclic carbonate of constituent element, formula 3 to formula 5 shown in the linear carbonate of constituent element, formula 2 There are the cyclic carbonate of unsaturated carbon bond, sultone and anhydride；

At least one during wherein R11 to R16 is hydrogen, halogen, alkyl or haloalkyl, and R11 to R16 is halogen or alkyl halide Base；

At least one during wherein R17 to R20 is hydrogen, halogen, alkyl or haloalkyl, and R17 to R20 is halogen or haloalkyl；

Wherein R21 and R22 is hydrogen or alkyl；

At least one during wherein R23 to R26 is hydrogen, alkyl, vinyl or aryl, and R23 to R26 is vinyl or aryl； With

Wherein R27 is alkylidene.

13. secondary cells according to claim 1, wherein electrolytic salt contain following at least one: lithium hexafluoro phosphate (LiPF₆), LiBF4 (LiBF₄), lithium perchlorate (LiClO₄), hexafluoroarsenate lithium (LiAsF₆) and formula 6 to formula 11 shown in Compound:

1 race's element during wherein X31 is long formula periodic chart or 2 race's element or aluminum；M31 is transition metal, long formula cycle 13 race's elements, 14 race's elements or 15 race's elements in table, R31 is halogen, Y31 is-(O=) C-R32-C (=O)-,-(O=) C- C(R33)₂-or-(O=) C-C (=O)-, R32 is alkylidene, halogeno alkylen, arlydene or halo arlydene, and R33 is alkane Base, haloalkyl, aryl or halogenated aryl, a3 is one in integer 1-4, and b3 is 0,2 or 4, and c3, d3, m3 and n3 are integers In 1-3 one；

1 race's element during wherein X41 is long formula periodic chart or 2 race's elements；M41 is in transition metal, long formula periodic chart 13 race's elements, 14 race's elements or 15 race's elements；Y41 is-(O=) C-(C (R41)₂)_b4-C (=O)-,-(R43)₂C-(C (R42)₂)_c4-C (=O)-,-(R43)₂C-(C(R42)₂)_c4-C(R43)₂-、-(R43)₂C-(C(R42)₂)_c4-S (=O)₂-、-(O =)₂S-(C(R42)₂)_d4-S (=O)₂-or-(O=) C-(C (R42)₂)_d4-S (=O)₂-, R41 and R43 is hydrogen, alkyl, halogen Or haloalkyl, at least one in R41 and R43 is halogen or haloalkyl respectively, and R42 is hydrogen, alkyl, halogen or alkyl halide Base, a4, e4 and n4 are integers 1 or 2, b4 and d4 is one in integer 1-4, and c4 is one in integer 0-4, and f4 and m4 is In integer 1-3 one；

1 race's element during wherein X51 is long formula periodic chart or 2 race's elements, M51 is in transition metal, long formula periodic chart 13 race's elements, 14 race's elements or 15 race's elements, Rf is that carbon number is the fluorinated alkyl of 1-10 or carbon number is the fluoro aryl of 1-10, bag Including two end values, Y51 is-(O=) C-(C (R51)₂)_d5-C (=O)-,-(R52)₂C-(C(R51)₂)_d5-C (=O)-,-(R52)₂C-(C(R51)₂)_d5-C(R52)₂-、-(R52)₂C-(C(R51)₂)_d5-S (=O)₂-,-(O=)₂S-(C(R51)₂)_e5-S (=O )₂-or-(O=) C-(C (R51)₂)_e5-S (=O)₂-, R51 is hydrogen, alkyl, halogen or haloalkyl, and R52 is hydrogen, alkyl, halogen Or haloalkyl, and at least one in them be halogen or haloalkyl, a5, f5 and n5 are 1 or 2, and b5, c5 and e5 are whole In number 1-4 one, d5 is one in integer 0-4, g5 and m5 is one in integer 1-3；

Formula 9

LiN(C_mF_2m+1SO₂)(C_nF_2n+1SO₂)…(9)

Wherein m and n is the integer of 1 or bigger；

Wherein R61 be carbon number be the perfluorinated alkylidene of the straight chain/side chain of 2-4, including two end values；

Formula 11

LiC(C_pF_2p+1SO₂)(C_qF_2q+1SO₂)(C_rF_2r+1SO₂)…(11)

Wherein, p, q and r are the integers of 1 or bigger.

14. secondary cells according to claim 1, wherein negative electrode contains the composite oxides shown in formula 12 as cathode active material Material:

Formula 12

LiNi_1-xM_xO₂…(12)

Wherein, M be cobalt, manganese, ferrum, aluminum, vanadium (V), stannum, magnesium (Mg), titanium, strontium (Sr), calcium (Ca), zirconium, molybdenum, technetium (Tc), ruthenium (Ru), In tantalum (Ta), tungsten, rhenium (Re), ytterbium (Yb), copper, zinc, barium (Ba), boron (B), chromium, silicon, gallium (Ga), phosphorus (P), antimony and niobium (Nb) At least one, and x is 0.005 ＜ x ＜ 0.5.

15. secondary cells according to claim 1, wherein anode active material layers between anode active material particles at least Portion gap has metal level.

16. secondary cells according to claim 15, wherein metal level covers at least part of surface of anode active material particles.

17. secondary cells according to claim 15, at least one during wherein metal level has ferrum, cobalt, nickel, zinc, copper and chromium Metallic element is as constituent element.

18. secondary cells according to claim 15, wherein the thickness of metal level is 1nm-30000nm, including two end values.

19. anodes, it can embed and deviate from electrode reaction thing and have anode active material layers in anode collector, its Described in anode active material layers comprise and multiple there is the silicon crystalline state anode active material particles as constituent element, and

The plurality of anode active material particles comprises spheroidal particle and aspherical particle, wherein the median size grain of spheroidal particle Footpath is 0.1 μm-40 μm, including two end values；And wherein the circularity of spheroidal particle is 0.5-1, including two end values.