CN101453034B - Battery and method of manufacturing the same - Google Patents
Battery and method of manufacturing the same Download PDFInfo
- Publication number
- CN101453034B CN101453034B CN2008101843409A CN200810184340A CN101453034B CN 101453034 B CN101453034 B CN 101453034B CN 2008101843409 A CN2008101843409 A CN 2008101843409A CN 200810184340 A CN200810184340 A CN 200810184340A CN 101453034 B CN101453034 B CN 101453034B
- Authority
- CN
- China
- Prior art keywords
- active material
- material layer
- anode active
- discharge
- offspring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
A battery capable of improving cycle characteristics is provided. An anode active material layer is formed by a vapor phase method, and includes Si as an element. In the anode active material layer, a plurality of primary particles formed by growth in a thickness direction are included, and the plurality of primary particles are agglomerated to form a plurality of secondary particles. Each secondary particle is separated by a groove formed by charge and discharge, and some of primary particles are split particles split by the groove. The average number of the split particles per secondary particle in 5 or more adjacent secondary particles is 10 or more. Moreover, the primary particles and the secondary particles are inclined to the same side.
Description
The application be that November 25, application number in 2005 are 200510126886.5 the applying date, exercise question divides an application for the application for a patent for invention of " Battery And Its Manufacturing Methods ".
The cross reference of related application
The present invention comprises the theme of the Japanese patent application JP2004-341182 that submits to Japan Patent office in the Japanese patent application JP 2004-341181 that relates on November 25th, 2004 and submit to Japan Patent office and on November 25th, 2004, and its full content is hereby incorporated by.
Technical field
The present invention relates to comprise the battery of anode active material layer, this anode active material layer comprises silicon (Si) as element, and relates to the manufacturing approach of this battery.
Background technology
In recent years, because mobile device has become more complicated and multi-functional, having required increases as the capacity of mobile device with the secondary cell of power supply.As the secondary cell that satisfies this requirement, enumerate lithium secondary battery.Yet in that at present the typical lithium and cobalt oxides that uses is as in anodal and the lithium secondary battery of graphite as negative pole, its battery capacity reaches saturation point, and it is very difficult therefore significantly increasing its capacity.Therefore, considered to use lithium metal (Li) as negative pole for a long time; Yet,, must improve lithium deposition/dissolved efficiency and control tree-shaped (dendritic) evaporation in order to make the actual use of this negative pole.
On the other hand, recently, positive carrying out the research of negative pole of use silicon, tin (Sn) etc. with high power capacity.But when recharge and discharge, because serious expansion and the contraction of active material, the negative pole with high power capacity is broken into small pieces, and current collection performance descends thus, and because the increase of surface area, the decomposition of acceleration electrolyte solution, so the non-constant of cycle characteristics.Therefore; Studied through vapor phase method, liquid phase method, roasting method (firing method) etc. and on collector body, formed the negative pole (for example, with reference to the open No.H8-50922 of Japanese Unexamined Patent Application, Japan Patent No.2948205 and the open No.H11-135115 of Japanese Unexamined Patent Application) that active material layer forms.Compare with the application type negative pole that forms through the slurry coating that will comprise granular active material, adhesive etc. in the prior art, this negative pole can prevent to be broken into small pieces, and in this negative pole, collector body and active material layer can form as a unit.Therefore, the electronic conductivity in the negative pole is excellent, and can be desirably in the more high-performance of capacity and cycle life aspect.This negative pole in addition, can reduce or eliminate the electric conductor, adhesive and the space that in the negative pole of prior art, exist, so can form film in essence.In addition, reported the rough surface that makes negative electrode collector, (for example can obtain excellent characteristic thus on the surface of negative active core-shell material, to form asperity; With reference to the open No.2002-83594 of Japanese Unexamined Patent Application, S.Fujitani, H.Yagi; K.Sayama, T.Yoshida, H.Tarui; Sanyo Electric Co., Ltd., " TheElectrochemical Society 203rd Meeting (Paris; France) Abstract 1152 ", (Newa-Si Alloy Thin Film Anode with Self Organized Micro Columnar Structure), P.1152; " Summary of Autumn Meeting of the Electrochemical Society ofJapan " 2002, p.107).
Summary of the invention
Yet, for example at S.Fujitani, H.Yagi, K.Sayama; T.Yoshida, H.Tarui, Sanyo Electric Co.; Ltd., " The Electrochemical Society 203rd Meeting (Paris, France) Abstract 1152 "; (New a-Si Alloy Thin Film Anode with Self OrganizedMicro Columnar Structure) is in this negative pole of P.1152 describing, in negative active core-shell material; Therefore the independent primary particle of on thickness direction, growing long and thinly in the initial stage of circulation, can obtain good relatively characteristic through charging and discharge reexpansion and contraction; But when repeating this circulation time, anode active material layer can be destroyed or break away from collector body, and characteristic descends thus.
This phenomenon often occurs in the situation of the poor adhesion between the primary particle wherein; But the adhesion between elementary particle is strong, and when offspring becomes too big thus, and offspring can come off owing to charging and discharge, or collector body can be destroyed, because be difficult to discharge the stress that expansion and contraction through offspring produce.Therefore, be difficult to obtain sufficient characteristic.
Consider the above, expectation provides and can prevent that anode active material layer from losing its shape and can improve the battery of battery behavior such as cycle characteristics, and the manufacturing approach of this battery.
According to an embodiment of the invention, a kind of battery is provided, comprising: positive pole; Negative pole; And electrolyte, wherein this negative pole is included in the anode active material layer on the negative electrode collector, and this anode active material layer comprises that silicon is as element; This anode active material layer comprises through a plurality of primary particles assembles a plurality of offsprings that form; In the direction, each offspring separates through groove in the plane of anode active material layer, and this groove has the degree of depth on the thickness direction of anode active material layer; Some primary particles are by the division particle (split particle) of groove division; And at least in the part anode active material layer, in 5 or more heterogeneous neighbour's offspring, the average of the division particle of each offspring is 10 or more.
According to another embodiment of the present invention, a kind of battery is provided, comprising: positive pole; Negative pole; And electrolyte; Wherein this negative pole is included in the anode active material layer on the negative electrode collector; This anode active material layer comprises that silicon is as element; This anode active material layer comprises through a plurality of primary particles assembles a plurality of offsprings that form; In the situation of the line that the 100 μ m of eight stripe pitch, 10 μ m of in 100 μ m * 70 mu m ranges in the part anode active material layer at least, drawing therein are long, the average of the offspring of every line is 5-11 (comprising end points), and the average of the primary particle of each offspring is 20 or more on line.
According to an execution mode more of the present invention, a kind of battery is provided, comprising: positive pole; Negative pole; And electrolyte; Wherein this negative pole is included in the anode active material layer on the negative electrode collector; This anode active material layer comprises that silicon is as element; This anode active material layer comprises through a plurality of primary particles assembles a plurality of offsprings that form, and tilts from the alignment the same side perpendicular to negative electrode collector in primary particle and the cross section of offspring on thickness direction.
According to an embodiment of the invention; A kind of method of making battery is provided; This battery comprises positive pole, negative pole and electrolyte; This method may further comprise the steps: through under 40nm/ second or bigger evaporation rate, evaporating, on negative electrode collector, form and comprise the anode active material layer of silicon as element.
In battery according to embodiment of the present invention; In 5 or more heterogeneous adjacent offspring; The average of the division particle of each offspring is 10 or more; Or in the battery of another execution mode according to the present invention, the average of the offspring of above-mentioned every line is 5-11 (comprising end points), and the average of the primary particle of each offspring is 20 or more on line; Therefore the adhesion between anode active material layer and the negative electrode collector can be improved, and the adhesion between the primary particle in anode active material layer can be improved.Therefore, can discharge owing to expands and shrinks the stress that causes, and can prevent that anode active material layer from losing its shape and disengaging negative electrode collector according to charging and discharge.Thereby, can improve battery behavior such as cycle characteristics.
Especially; In 10 continuous offsprings; When being 50% or more for a long time wherein at quantity ratio perpendicular to the offspring longer of the length on the direction of thickness direction than the length on the thickness direction; Or the thickness of anode active material layer be in the reference charging and during the discharge before discharging 1.7 times of thickness or more hour during the discharge after repeating reference (reference) charging and discharge, can obtain higher effect.
In addition; When initial charge is inserted anode active material layer with lithium before with discharge; Or when the electro-chemical activity lithium remains in the anode active material layer after discharge; Can further discharge owing to expand and shrink the stress that causes, and can further improve battery behavior such as cycle characteristics according to charging and discharge.
According to the present invention again in the battery of an execution mode; Primary particle and offspring tilt to the same side; Therefore can discharge owing to expands and shrinks the stress that causes, and can prevent that anode active material layer from losing its shape and disengaging negative electrode collector according to charging and discharge.Thereby, can improve battery behavior such as cycle characteristics.
Especially, when elementary particle and offspring from perpendicular to the line of negative electrode collector angle tilt with 5 °-60 °, can obtain higher effect.
In method according to the manufacturing battery of embodiment of the present invention; Through evaporating with 40nm/ second or bigger evaporation rate; Form anode active material layer, therefore can easily improve adhesion and the adhesion between the primary particle in anode active material layer between anode active material layer and the negative electrode collector.Thereby, can easily make battery according to this execution mode.
Of the present invention other will embody from following description with further purpose, feature and advantage more completely.
Description of drawings
Fig. 1 is the cutaway view according to the secondary cell of first embodiment of the invention;
Fig. 2 is the SEM photo of the particle structure of the anode active material layer of displaying secondary cell shown in Figure 1;
Fig. 3 is for describing the diagram of SEM photo shown in Figure 2;
Fig. 4 is the SEM photo of the cross-section structure of displaying anode active material layer shown in Figure 2;
Fig. 5 is for describing the diagram of SEM photo shown in Figure 4;
Fig. 6 is the SIM photo of the amplifier section of displaying anode active material layer shown in Figure 2;
Fig. 7 is for describing the diagram of SIM photo shown in Figure 6;
Fig. 8 is the decomposition diagram according to the secondary cell of second embodiment of the invention;
Fig. 9 is the cutaway view along the secondary cell of the line I-I of Fig. 8;
Figure 10 is the SEM photo of displaying according to the particle structure of the anode active material layer of the 3rd execution mode of the present invention;
Figure 11 is the sketch map of the particle structure of anode active material layer shown in Figure 10;
Figure 12 is the SEM photo of displaying according to the particle structure on the surface of the anode active material layer of embodiment 1-4;
Figure 13 is the SEM photo of displaying according to the particle structure on the surface of the anode active material layer of comparative example 1-2;
Figure 14 is the SEM photo of displaying according to the particle structure on the surface of the anode active material layer of comparative example 3;
Figure 15 is the SEM photo of displaying according to the particle structure of the section of the anode active material layer of comparative example 3;
Figure 16 is the amplification SIM photo of displaying according to the particle structure on the surface of the anode active material layer of comparative example 3;
Figure 17 is the SEM photo of displaying according to the particle structure on the surface of the anode active material layer of comparative example 3;
Figure 18 is the SEM photo of displaying according to the particle structure of the section of the anode active material layer of comparative example 3;
Figure 19 is the amplification SIM photo of displaying according to the particle structure on the surface of the anode active material layer of comparative example 3; And
Figure 20 is the SEM photo of displaying according to the particle structure of the anode active material layer of comparative example 5-1.
Embodiment
Describe in detail preferred embodiment below with reference to accompanying drawing.
(first execution mode)
Fig. 1 has showed the structure according to the secondary cell of first embodiment of the invention.This secondary cell is so-called Coin shape, and in this secondary cell, will be included in the packing cap (package cup) 11 negative pole 12 be included in positive pole 14 in the pack case (package can) 13 with barrier film 15 laminations in the centre.The marginal portion of packing cap 11 and pack case 13 are passed through insulating cell 16 calkings with sealing negative pole 12 and anodal 14.Packing cap 11 and pack case 13 by, for example, metal such as stainless steel or aluminium (Al) are processed.
This negative electrode collector 12A is preferably processed by the metal material that comprises at least a metallic element, and it does not form intermetallic compound with lithium.This is because when metal material and lithium formation intermetallic compound; Negative electrode collector 12A expands or shrinks according to charging and discharge; The structural deterioration of anticathode collector body 12A takes place thus; Therefore the current collection performance of negative electrode collector 12A descends, and negative electrode collector 12A supports the ability reduction of anode active material layer 12B.In specification, metal material not only comprises the simple substance of metallic element, also comprises the alloy that contains two or more metallic elements and contains one or more metallic elements and the alloy of one or more metalloid elements.The instance that does not form the metallic element of intermetallic compound with lithium comprises copper (Cu), nickel (Ni), titanium (Ti), iron (Fe) and chromium (Cr).
The surface roughness of negative electrode collector 12A is preferably 1 μ m or bigger in roughness distributes 10 height (ten point heightof roughness profile) Rz; And arithmetic average roughness Ra is 0.15 μ m or bigger, because can improve the adhesion of anode active material layer 12B.
Anode active material layer 12B comprises silicon as element, because silicon has big insertion and deviates from the ability of lithium and can obtain high-energy-density.Can simple substance, the form of alloy or compound comprises silicon.
Anode active material layer 12B forms through for example vapor phase method, and comprises a plurality of primary particles that form through growth on thickness direction.A plurality of primary particles are assembled a plurality of offsprings of formation.
Fig. 2 is scanning electron microscopy (SEM) photo (secondary electron image) of the particle structure on the surface of displaying anode active material layer 12B, and Fig. 3 is for describing the diagram of Fig. 2.Fig. 4 is the SEM photo of the section of displaying anode active material layer 12B shown in Figure 2, and Fig. 5 is for describing the diagram of Fig. 4.Fig. 6 is scanning ion microscope (SIM) photo of the discharge portion of exploded view 2, and Fig. 7 is for describing the diagram of Fig. 6.In Fig. 2, each hatched area shown in Figure 3 offspring 121 of respectively doing for oneself, and in offspring 121, each particle shape part primary particle of respectively doing for oneself.In addition, in Fig. 4, the hatched area of Fig. 5 is the section of primary particle 123.
Shown in Fig. 2-7, on the direction, each offspring 121 was opened through the groove that on the thickness direction of anode active material layer 12B, has the degree of depth in 122 minutes in the plane of anode active material layer 12B.In addition, shown in Figure 4 and 5, primary particle 123 is not only adjacent one another are, and part combines with formation offspring 121 each other, and groove 122 almost arrives negative electrode collector 12A.For example, the degree of depth of groove 122 is about 5 μ m or bigger, and the width of groove 122 is for example about 1 μ m or bigger.Groove 122 forms through charging and discharge, and groove 122 is not along primary particle but formation relatively linearly.Thereby as amplifying down shown in Figure 6, some primary particles are the division particle 124 that is divided by groove 122.In Fig. 7, (knurled) of annular knurl zone is division particle 124.
The average of the division particle 124 of each offspring in 5 or more heterogeneous adjacent offspring is preferably 10 or more; Be combined together to form and have certain size or bigger offspring 121 because have the primary particle 123 of certain degree of adhesion, can discharge thus owing to expand and shrink the stress that causes according to charging and discharge.The core that is desirably in negative pole 12 satisfies the average of division particle 124, because electric current is easy to focus on the marginal portion, and the variation in the formation of groove 122 is easy to take place.
In addition; Size as offspring 121; The spacing of in perpendicular to 100 μ m * 70 mu m ranges in the plane of thickness direction, drawing therein is in the situation of the long line of eight the 100 μ m of 10 μ m; The average of the offspring 121 of every line is preferably 5-11 (comprising end points), and the average of the primary particle 123 of each offspring 121 is preferably 20 or more on line, because can discharge owing to expanding and shrinking the stress that causes through being divided into the offspring 121 with this size.As the situation of the quantity of above-mentioned division particle 124, can satisfy the quantity of offspring 121 and the quantity of primary particle 123 at the core of negative pole 12.The width of line is under the situation of 1 μ m therein, and the offspring that is arranged on the line of part is included in the quantity that is present in the offspring on the line at least, even and an offspring be positioned on the many lines, this offspring can be included in each bar of these many lines.In addition, division particle 124 is included in the quantity of the primary particle that offspring comprises.
In addition; Size as offspring 121; In the section of the thickness direction shown in the Figure 4 and 5; Wherein in 10 continuous offsprings 121, perpendicular to the quantity of the length T on the direction of thickness direction 2 offspring longer than the length T on thickness direction 1 than being preferably 50% or more.This is because in this case, can further discharge stress.As the situation of the quantity of above-mentioned division particle 124, can satisfy this quantity ratio at the core of negative pole 12.Measurement in the section of each offspring 121 in the maximum of the length T on the thickness direction 1 with in maximum perpendicular to the length T on the direction of thickness direction 2.
For example, can observe these particle structures through SEM shown in Fig. 2 and 4 or SIM as shown in Figure 6.In addition, anode active material layer 12B preferably cuts to observe section through FIB (FIB) or slicing machine.
In secondary cell; Can prevent because the expansion of the anode active material layer 12B that recharge and discharge cause through this particle structure; And for example; 40 chargings therein and discharge cycles are under the situation of reference charging and discharge, when the thickness of anode active material layer 12B be the discharge before reference charging and discharge during discharge after repeating reference charging and discharge 1-1.7 times of thickness.In this case, on charging and discharge battery at least once, carry out reference charging and discharge.But in the initial stage of charging and discharge, the state variation of anode active material layer 12B is very big, therefore preferably charge after the battery assembling and discharge 20 times or still less battery on carry out reference charging and discharge.The thickness of anode active material layer 12B is the mean value of the length T 1 on the thickness direction in the section of 10 continuous quadratic particles 121 of the core of negative pole 12.Measure length T 1 as stated.For example, when on the two sides that anode active material layer is configured in negative electrode collector, measure the length T 1 on the thickness direction of 10 continuous quadratic particles 121 on each face, and the mean value of definite length T 1.
Anode active material layer 12B preferred at least with the part of negative electrode collector 12A at the interface with negative electrode collector 12A alloying.More particularly; The Elements Diffusion of preferred negative electrode current collector 12A is advanced among the anode active material layer 12B; Or the Elements Diffusion of anode active material layer 12B is advanced among the negative electrode collector 12A; Or they are diffused into each other between it at the interface, even because anode active material layer 12B expands according to charging and discharge and shrinks, also can prevent anode active material layer 12B disengaging negative electrode collector 12A.
In addition, preferably before initial charge and discharge, lithium is inserted among the anode active material layer 12B in advance.This is because can further discharge owing to expand and shrink the stress on the negative electrode collector 12A that is applied to that causes, and can increase through with the lithium of electrolyte solution reaction consumes, and can prevent the rising of negative pole 12 voltages in the later stage of discharge.In this case, in the initial stage of charge-discharge cycles, the electro-chemical activity lithium preferably remains in after charging in the negative pole 12 at least.
For example; Can take out negative pole 12 through after discharge, taking secondary cell apart; Use the conducts such as metal forming that lithium metal can deposit on it that electrode is formed half-cell; And detect lithium and whether can shift out with lithium metal from negative pole 12 and whether can deposit electrode, confirm whether the electro-chemical activity lithium remains in the negative pole 12.
Anode active material layer 14B for example comprises, be selected from the positive electrode that can insert and deviate from lithium one or both or multiple as positive electrode active materials, and if necessary, can comprise electric conductor such as raw material of wood-charcoal material and adhesive such as polyvinylidene fluoride.As the positive electrode that can insert and deviate from lithium, for example, preferably by general formula Li
xMIO
2Expression contain lithium-metal composite oxides can produce high voltage and have high density because contain lithium-metal composite oxides, therefore through containing the more high power capacity that lithium-metal composite oxides can obtain secondary cell.In formula, MI representes one or more transition metal, and for example, is selected from least a preferably as MI of cobalt (Co) and nickel.The value of x depends on the charging-discharge condition of battery, and usually in the scope of 0.05≤x≤1.10.This instantiation that contains lithium-metal composite oxides comprises LiCoO
2, LiNiO
2Deng.
As electrolytic salt, for example, enumerate for example LiPF of lithium salts
6, LiCF
3SO
3Or LiClO
4Can use the mixture of a kind of electrolytic salt or two or more electrolytic salts.
For example, make battery through following steps.
At first, form on negative electrode collector 12A through for example vapor phase method and comprise the anode active material layer 12B of silicon as element.As vapor phase method; For example; Use physical deposition method or chemical deposition, and more particularly, can use vacuum vapor deposition method, sputtering method, ion plating, laser ablation (laserablation) method, CVD (chemical vapour deposition (CVD)) method, spraying (spraying) method etc.After forming anode active material layer 12B, under vacuum atmosphere or non--oxidizing atmosphere, heat-treat.Thereby, can carry out the alloying of negative electrode collector 12A and anode active material layer 12B, and can improve the adhesion of primary particle 123, and can form above-mentioned particle structure through charging and discharge.Then, if necessary, lithium electrochemical is inserted among the anode active material layer 12B through for example vacuum vapor deposition method.Can before heat treatment, insert lithium.
Next, on positive electrode collector 14A, form anode active material layer 14B.For example, positive electrode active materials and electric conductor if necessary and adhesive are mixed forming mixture, and this mixture is coated on positive electrode collector 14A.Then, this mixture compression molding is formed anode active material layer 14B.Afterwards, with negative pole 12, barrier film 15 and anodal 14 laminations, and they are placed packing cap 11 and pack case 13, and inject electrolyte solution, to packing cap 11 and pack case 13 calkings with assemble.After assemble, to battery charge and discharge in anode active material layer 12B, to form above-mentioned particle structure.
In addition, even under the situation that anode active material layer 12B forms through the evaporation with 40nm/ second or higher evaporation rate therein, can obtain above-mentioned particle structure.In this case, after forming anode active material layer 12B, can further carry out or not heat-treat.
When battery charge, lithium ion is deviate from from positive pole 14, inserts in the negative pole 12 through electrolyte solution.When secondary cell discharged, for example, lithium ion was deviate from from negative pole 12, inserted in anodal 14 through electrolyte solution.Anode active material layer 12B significantly expands and shrinks according to charging and discharge, yet anode active material layer 12B has above-mentioned particle structure, so primary particle 123 is not individually but on offspring 121 bases, expands or shrink.Thereby, can discharge stress, and can prevent that anode active material layer 12B from losing its shape and breaking away from negative electrode collector 12A.
Therefore; In this embodiment; In anode active material layer 12B; In 5 or more heterogeneous adjacent offspring, the average of the division particle 124 of each offspring is 10 or more, or the average of the offspring 121 of above-mentioned every line is 5-11 (comprising end points); Therefore and the average of the primary particle 123 of each offspring 121 is 20 or more, can improve adhesion and the adhesion between the primary particle in anode active material layer 12B 123 between anode active material layer 12B and the negative electrode collector 12A.Thereby, can discharge owing to expands and shrinks the stress that causes, and can prevent that anode active material layer 12B from losing its shape and disengaging negative electrode collector 12A according to charging and discharge.Therefore, can improve battery behavior such as cycle characteristics.
Especially; In the section on thickness direction; When wherein perpendicular to the quantity of the length T on the direction of thickness direction 2 offspring longer than the length T on thickness direction 1 than being 50% or more; Or the thickness of anode active material layer 12B be in the reference charging and during the discharge before discharging 1.7 times of thickness or more hour during the discharge after repeating reference charging and discharge, can obtain higher effect.
In addition; When initial charge is inserted anode active material layer 12B with lithium before with discharge; Or when the electro-chemical activity lithium remains among the anode active material layer 12B after discharge; Can further discharge owing to expand and shrink the stress that causes, thereby can further improve battery behavior such as cycle characteristics according to charging and discharge.
In addition; When forming anode active material layer 12B, can easily improve adhesion and the adhesion between the primary particle in anode active material layer 12B 123 between anode active material layer 12B and the negative electrode collector 12A through evaporation with 40nm/ second or bigger evaporation rate.Thereby, can easily make secondary cell according to this execution mode.
(second execution mode)
Fig. 8 has showed the structure according to the secondary cell of second embodiment of the invention.In this secondary cell, be connected with lead-in wire 21 and 22 spiral winding electrode 20 and be included in film-shape packaging element 30, can form thus have smaller szie, the more light weight and the secondary cell of low profile (lower profile) more.
Lead-in wire 21 is for example guided the outside with identical direction into from the inside of packaging element 30 with 22.The lead-in wire 21 and 22 by, for example, sheet or netted metal material such as aluminium, copper, nickel or stainless steel are processed.
In addition, packaging element 30 can replace above-mentioned aluminium lamination press mold to form by the laminated film with any other structure, high molecular weight membrane such as polypropylene or metal film.
Fig. 9 has showed along the cutaway view of the spiral winding electrode 20 of the line I-I of Fig. 8.Spiral winding electrode 20 is to comprise negative pole 23 with positive pole 24 and at the barrier film 25 of centre and the screw winding laminate of dielectric substrate 26, and the most external of spiral winding electrode 20 is with boundary belt 27 protections.
For example, can make secondary cell through following steps.
At first, as first execution mode, form negative pole 23 and positive pole 24, and on negative pole 23 and anodal 24, form the wherein dielectric substrate 26 of supporter maintenance electrolyte solution.Then, will go between and 21 and 22 be connected respectively to negative electrode collector 23A and positive electrode collector 24A.Then; The negative pole 23 that is formed with dielectric substrate 26 on it with its on be formed with dielectric substrate 26 positive pole 24 after barrier film 25 laminations in the centre form laminate; With this laminate screw winding, and the most external that boundary belt 27 is attached to laminate is to form spiral winding electrode 20.Afterwards, spiral winding electrode 20 is clipped between the packaging element 30, and the marginal portion of packaging element 30 is adhering to each other so that spiral winding electrode 20 is sealed in the packaging element 30 through thermofussion welding etc.At this moment, with adhesive film 31 insert lead-in wire 21 and 22 and packaging element 30 between.
In addition, can pass through the following steps assemble.At first, the same with first execution mode, after forming negative pole 23 and anodal 24, connect lead-in wire 21 and 22.Then, negative pole 23 and positive pole 24 and barrier film 25 laminations in the centre are formed laminate, and with this laminate screw winding.The most external that boundary belt 27 is attached to the screw winding laminate is to form the screw winding body as the precursor of spiral winding electrode 20.Next, the screw winding body is clipped between the packaging element 30, and the marginal portion of packaging element 30 is packed with the shape pouch through the thermofussion welding adhesion except that a side.Then, will comprise electrolyte solution, inject packaging element 30 as the monomer of the material of high-molecular weight compounds and the electrolyte of polymerization initiator and any other materials if necessary such as polymerization inhibitor with component.Afterwards, under vacuum atmosphere, pack the open section of element 30, and make monomer polymerization form high-molecular weight compounds, form gel electrolyte layer 26 thus through applying heat through thermofussion welding.
Thereby, after assemble, as first execution mode, to battery charge and discharge in anode active material layer 23B, to form above-mentioned particle structure.
This secondary cell works as in the first embodiment, and has those the identical effects with first execution mode.
(the 3rd execution mode)
Secondary cell according to the 3rd execution mode has the structure the same with first execution mode, except the structure difference of anode active material layer 12B.Therefore, in this embodiment, with reference to figure 1, identical component, and is not described further as first execution mode with identical numeral.
Anode active material layer 12B comprises silicon as element, because silicon has big insertion and deviates from the ability of lithium and can obtain high-energy-density.Form with simple substance, alloy or compound comprises silicon.
Anode active material layer 12B forms through for example vapor phase method, and comprises a plurality of primary particles that form through growth on thickness direction.A plurality of primary particles are assembled a plurality of offsprings of formation.
Figure 10 is the SEM photo of the particle structure of the section of displaying anode active material layer 12B, and Figure 11 is the sketch map of particle structure.Shown in Figure 10 and 11, each offspring 121 was opened through groove in 122 minutes.Groove 122 is through for example charging and the formation of discharging, and almost arrives negative electrode collector 12A.Primary particle 123 is not only adjacent one another are simply, and is bonded to each other at least in part to form offspring 121.Tilt from alignment the same side in primary particle 123 and the cross section of offspring 121 on thickness direction perpendicular to negative electrode collector 12A.Thereby, in secondary cell, can discharge owing to expand and shrink the stress that causes according to charging and discharge.And, can reduce the expansion of thickness direction.
For example, shown in figure 10, can observe this particle structure through SEM or SIM.In addition, cut anode active material layer 12B to observe the cross section through FIB or slicing machine.
Anode active material layer 12B preferred at least with the part of negative electrode collector 12A at the interface with negative electrode collector 12A alloying.More particularly; The Elements Diffusion of preferred negative electrode current collector 12A is advanced among the anode active material layer 12B; Or the Elements Diffusion of anode active material layer 12B is advanced among the negative electrode collector 12A; Or they are diffused into each other between it at the interface, even because anode active material layer 12B expands according to charging and discharge and shrinks, also can prevent anode active material layer 12B disengaging negative electrode collector 12A.
For example, can make secondary cell through following steps.
At first, form on negative electrode collector 12A through for example vapor phase method and comprise the anode active material layer 12B of silicon as element.As vapor phase method, for example, use the vapor phase method of describing in the first embodiment.At this moment, for example, with respect to the normal of negative electrode collector 12A with an angle injection material.Thereby the primary particle of anode active material layer 12B is with respect to the angle growth of normal to tilt of negative electrode collector 12A.Then, if necessary, under vacuum atmosphere or non--oxidizing atmosphere, heat-treat.
Next, as in the first embodiment, on positive electrode collector 14A, form anode active material layer 14B, and with negative pole 12, barrier film 15 and anodal 14 laminations.Then, they are placed packing cap 11 and pack case 13, and inject electrolyte solution.Then, to packing cap 11 and pack case 13 calkings with assemble.After assemble, to battery charge and discharge in anode active material layer 12B, forming groove 122, thereby be divided into offspring 121.
When secondary cell charge, lithium ion is deviate from from positive pole 14, inserts in the negative pole 12 through electrolyte solution.When secondary cell discharged, for example, lithium ion was deviate from from negative pole 12, inserted in anodal 14 through electrolyte solution.Anode active material layer 12B significantly expands and shrinks according to charging and discharge; Yet primary particle 123 tilts to the same side with offspring 121, therefore can discharge stress, and can prevent that anode active material layer 12B from losing its shape and breaking away from negative electrode collector 12A.
Therefore; In this embodiment; Primary particle 123 and the offspring 121 of anode active material layer 12B tilt to the same side; Therefore can discharge owing to expands and shrinks the stress that causes, and can prevent that anode active material layer 12B from losing its shape and disengaging negative electrode collector 12A according to charging and discharge.Thereby, can improve battery behavior such as cycle characteristics.
Especially, when elementary particle 123 and offspring 121 from during with the angle tilt of 5 °-60 ° (comprising end points), obtaining higher effect perpendicular to the line of negative electrode collector 12A.
(the 4th execution mode)
Secondary cell according to the 4th execution mode has the structure identical with second execution mode, except anode active material layer 12B has the structure identical with the 3rd execution mode.That is, in the secondary cell with structure shown in Fig. 8 and 9, anode active material layer 12B has the structure identical with the 3rd execution mode.This secondary cell is as working in the 3rd execution mode, and has those the identical effects with the 3rd execution mode.Therefore especially, in this embodiment, can prevent the expansion of anode active material layer 23B on thickness direction,, also can prevent the expansion of battery even when recharge is with discharge.
[embodiment]
Describe specific embodiment of the present invention in detail below with reference to accompanying drawing.
(embodiment 1-1 to 1-7)
Formation has the secondary cell of structure shown in Fig. 8 and 9.
At first, on the surface of Copper Foil, to form particle diameter be that the thin copper particle of about 2 μ m is the negative electrode collector 23A of about 2.8 μ m with preparation roughness 10 the height Rz that distribute through electroplating.Then, on negative electrode collector 23A, forming the thickness of being processed by silicon through the electron beam vacuum vapor deposition method is the anode active material layer 23B of about 5.5 μ m.At this moment, as shown in table 1 in embodiment 1-1 to 1-7, in 0.5nm/ second-100nm/ scope second, change film and form speed.Next, in embodiment 1-1 to 1-3,1-5 and 1-7, in reduced pressure atmosphere, under 300 ℃, heat-treat.In embodiment 1-4 and 1-6, do not heat-treat.
In addition, be the lithium and cobalt oxides (LiCoO of 5 μ m with 92 weight portions as the average grain diameter of positive electrode active materials
2) powder, 2 weight portions mix as the polyvinylidene fluoride of adhesive as the carbon black of electric conductor and 5 weight portions and form mixture, and the N-N-methyl-2-2-pyrrolidone N-that this mixture is put into as decentralized medium forms slurry.Then, this slurry is coated on the positive electrode collector 24A that the thickness of being processed by aluminium foil is 15 μ m, and dry, suppress this slurry then and form anode active material layer 24B.
Next, with 37.5 weight % ethylene carbonates, 37.5 weight % propylene carbonates, 10 weight % vinylene carbonates and 15 weight %LiPF
6Mixing is with the preparation electrolyte solution; And will wherein be mixed with 30 weight % electrolyte solutions, 10 weight % are 600 as the weight average molecular weight of block copolymer; The precursor solution of 000 polyvinylidene fluoride and 60 weight % dimethyl carbonates is coated on the two sides of negative pole 23 and positive pole 24; And make the dimethyl carbonate volatilization, thereby form dielectric substrate 26.
Afterwards, connect lead-in wire 21 and 22, and with negative pole 23 and positive pole 24 with barrier film 26 laminations in the centre, and screw winding.Negative pole 23 is sealed in the packaging element of being processed by the aluminium lamination press mold 30 with anodal 24, thereby has assembled secondary cell.
As comparative example 1-1 to 1-3 with respect to embodiment 1-1 to 1-7; As shown in table 1; Equally assemble secondary cell with embodiment 1-1 to 1-7; Except forming speed, the film of anode active material layer 23B in the scope of second 0.5nm/ second-20nm/, changes, and beyond after forming anode active material layer 23B, not heat-treating.
Under 25 ℃ condition, to the secondary cell of embodiment 1-1 to 1-7 and comparative example 1-1 to 1-3 charge-discharge test to be to measure the 101st circulation to the capability retention of circulation for the second time.At this moment, at constant current density 1mA/cm
2Down secondary cell charge is reached 4.2V up to cell voltage, under constant voltage 4.2V, secondary cell charge is reached 0.05mA/cm up to current density then
2Then, at constant current density 1mA/cm
2Discharge reaches 2.5V up to cell voltage to secondary cell down.Under the situation of secondary cell charge, the capacity utilance of negative pole 23 is 90% therein, and prevents the deposition of lithium metal on negative pole 23.The discharge capacity of capability retention through the 101st circulation calculated the ratio of the discharge capacity of circulation for the second time, that is, and and (discharge capacity that circulate the discharge capacity of the 101st circulation/second time) * 100.
In addition; Under identical condition to the secondary cell charge of embodiment 1-1 to 1-7 and comparative example 1-1 to 1-3 and discharge ten times; Take battery then apart and take out the negative pole 23 under the discharge condition; And, observe the surface of negative pole 23 and the section of core through SIM then with dimethyl carbonate cleaning negative pole 23.The core that cuts negative pole 23 through FIB is to observe section.Through the SIM photo that use obtains, confirm the average of the division particle 124 of each offspring 121 in 5 adjacent offsprings 121, therein in 100 μ m * 70 mu m ranges, draw spacing be the offspring 121 of every line in the situation of the long line of eight 100 μ m of 10 μ m average, each offspring 121 primary particle 123 average and in ten continuous quadratic particles 121 wherein at ratio perpendicular to the length T on the direction of thickness direction 2 offspring longer than the length T on thickness direction 1.
In addition; In the secondary cell of embodiment 1-1 to 1-7 and comparative example 1-1 to 1-3; With charging under the same conditions and ten times the battery of discharging is regarded the battery before reference charging and discharge as, and 40 times the battery of will charging under the same conditions and discharge ten times and further charge under the same conditions then and discharge is regarded the battery after reference charging and discharge as.To before reference charging and discharge, take apart to take out the negative pole 23 under the discharge condition with each battery afterwards.Afterwards, clean negative pole 23, and observe the section of negative pole 23 cores through SEM or SIM with dimethyl carbonate.Through using SEM photo or SIM photo; Ten continuous quadratic particles 121 the length T 1 on thickness direction of measurement on the two sides of negative electrode collector 23A; And measure the thickness of their mean value, and be determined at after reference charging and the discharge the coefficient of expansion to the anode active material layer 23B before reference charging and discharge as anode active material layer 23B.
These results are shown in Table 1.Fig. 2 that has described and 4 is the SEM photo of the anode active material layer 23B of embodiment 1-2, and Fig. 6 is the SIM photo of the anode active material layer 23B of embodiment 1-2.In addition, the SEM photo on the anode active material layer 23B of embodiment 1-4 surface is shown in figure 12, and the SEM photo on the anode active material layer of comparative example 1-2 surface is shown in figure 13.
Table 1
As shown in table 1,1-1 to 1-3 compares with comparative example, in embodiment 1-1 to 1-7, obtains higher capability retention.In addition; Like table 1 and Fig. 2,4, shown in 6 and 10, in the negative pole 23 of embodiment 1-1 to 1-7, division particle 124 averages are 10 or more; And the average of offspring 121 is 5-11 (comprising end points); And the average of primary particle 123 is 20 or more, and wherein perpendicular to the quantity of the length T on the direction of thickness direction 2 offspring longer than the length T on the thickness direction 1 than being 50% or more, and the coefficient of expansion of anode active material layer 23B is 1.7 times or littler.On the other hand, shown in figure 13 in comparative example 1-1 to 1-3, anode active material layer comes off, and therefore can't observe particle state.
That is, find to improve cycle characteristics when the particle state of anode active material layer 23B as stated the time.In addition, find that this particle state can be easily through heat-treating or obtaining through forming anode active material layer 23B with 40nm/ second or higher film formation speed evaporation after forming anode active material layer 23B.
(embodiment 2)
Equally assemble secondary cell with embodiment 1-2, except inserting lithium among the anode active material layer 23B in advance.At this moment, through after forming anode active material layer 23B, making the lithium evaporation of metal to anode active material layer 23B surface and heat-treat and insert lithium.The amount of the lithium that inserts is 5% of negative pole 23 capacity.In this case, another test through carrying out in advance proves that the electro-chemical activity lithium remains in the negative pole 23 in the initial stage of charge-discharge cycles after discharge.
Situation with embodiment 1-2 is the same, to secondary cell charge and the discharge of embodiment 2, and measures the capability retention of the 101st circulation, and observes the particle state of anode active material layer 23B in an identical manner.The result is shown in Table 2 with the result of embodiment 1-2.
Table 2
As shown in table 2, compare with embodiment 1-2, in embodiment 2, obtain higher capability retention.That is, discovery or when the electro-chemical activity lithium is residual after discharge, can further improve cycle characteristics when lithium being inserted in the negative pole 23 in advance
(embodiment 3 and 4)
In embodiment 3, equally assemble secondary cell with embodiment 1-1 to 1-7, except replace vacuum vapor deposition method formation anode active material layer 23B through the CVD method after, insert lithium, the step of going forward side by side carries out beyond the heat treatment.In embodiment 4, equally assemble secondary cell with embodiment 1-1 to 1-7, except replace vacuum vapor deposition method formation anode active material layer 23B through sputtering method after, insert lithium, the step of going forward side by side carries out beyond the heat treatment.
As comparative example 3 and 4 with respect to embodiment 3 and 4, with the same secondary cell that assembles of embodiment 3 with 4, except not inserting lithium, and beyond not heat-treating.
The same with embodiment 1-1 to 1-7, to embodiment 3 and 4 and the secondary cell charge and the discharge of comparative example 3 and 4, and measure the capability retention of the 101st circulation, and observe the particle state of anode active material layer 23B in an identical manner.The result is shown in the table 3 and 4.The SEM photo of the anode active material layer of comparative example 3 is shown in Figure 14 and 15; And the SIM photo of the anode active material layer of comparative example 3 is shown in figure 16; With the SEM photo of the anode active material layer of comparative example 4 shown in Figure 17 and 18, and the SIM photo of the anode active material layer of comparative example 4 is shown in figure 19.
Table 3
Table 4
Shown in table 3 and 4, compare with 4 with comparative example 3, in embodiment 3 and 4, obtain higher capability retention.In addition; In the negative pole 23 of embodiment 3 and 4; The average of division particle 124 is 10 or more, and the average of offspring 121 is 5-11 (comprising end points), and primary particle average is 20 or more; And wherein perpendicular to the quantity of the length T on the direction of thickness direction 2 offspring 121 longer than the length T on the thickness direction 1 than being 50% or more, and the coefficient of expansion of anode active material layer 23B is 1.7 times or littler.On the other hand, in comparative example 3 and 4, shown in Figure 12 to 17, a little less than the adhesion of primary particle, and most of offspring is divided into small pieces along primary particle, and particle state is outside above-mentioned scope.
That is,, also can form the particle state of aforesaid anode active material layer 23B, and can improve cycle characteristics even find to form anode active material layer 23B through other method.
(embodiment 5-1 to 5-7)
Equally assemble secondary cell with embodiment 1-1 to 1-7, except the structure that changes negative pole 23.Through on the negative electrode collector 23A of the rough surface of being processed by Copper Foil that has thickness 22 μ m and form through the electron beam vacuum vapor deposition method, forming the thickness of being processed by silicon is the anode active material layer 23B of about 9 μ m; And under reduced atmosphere, heat-treat, form negative pole 23.At this moment, change wherein is injected into the angle on the negative electrode collector 23A with material in embodiment 5-1 to 5-7.
Comparative example 5-1 as with respect to embodiment 5-1 to 5-7 equally assembles secondary cell with embodiment 5-1 to 5-7, except when when forming anode active material layer, beyond the angle injection material perpendicular to negative electrode collector.
Under 25 ℃ condition, to the secondary cell of embodiment 5-1 to 5-7 and comparative example 5-1 charge-discharge test to be to confirm that the 31st circulation is to the capability retention of circulation for the second time.At this moment, at constant current density 1mA/cm
2Down secondary cell charge is reached 4.2V up to cell voltage, under constant voltage 4.2V, secondary cell charge is reached 0.05mA/cm up to current density then
2Then, at constant current density 1mA/cm
2Discharge reaches 2.5V up to cell voltage to secondary cell down.Under the situation that secondary cell is recharged therein, the capacity utilance of negative pole 23 is 90%, and prevents the deposition of lithium metal on negative pole 23.The discharge capacity of capability retention through the 31st circulation calculated the ratio of the discharge capacity of circulation for the second time, that is, and and (discharge capacity that circulate the discharge capacity of the 31st circulation/second time) * 100.
In addition; In the secondary cell of embodiment 5-1 to 5-7 and comparative example 5-1; Thickness and the thickness after 31 chargings and discharge cycles of measuring (at 0 circulation time) before charging and the discharge to be confirming range of expansion, and through the range of expansion rate (expansion range rate) of mathematical expression 1 calculating for comparative example 5-1.
(mathematical expression 1)
Range of expansion rate=[(A-B)/(a-b)] * 100
In mathematical expression 1, A is the thickness of each embodiment before charging and discharge, and B be at the thickness of charging and each embodiment of discharge back and a thickness for comparative example 5-1 before charging and discharge, and b be charge and discharge after the thickness of comparative example 5-1.
In addition, take out the negative pole 23 under the discharge condition at each secondary cell of taking embodiment 5-1 to 5-7 and comparative example 5-1 after the 31st circulation apart, and clean negative pole 23, observe the section of the core of negative pole 23 then through SEM with dimethyl carbonate.The core that cuts negative pole 23 through slicing machine is to observe section.The SEM photo that obtains through use in 5 continuous offsprings 121, is measured primary particle 123 and offspring 121 from the angle θ perpendicular to the line of negative electrode collector 23A, and measures their mean value.
These results are shown in Table 5.The Figure 10 that has described is the SEM photo of the anode active material layer 23B of embodiment 5-1.In addition, the SEM photo of the anode active material layer of comparative example 5-1 is shown in figure 20.
Table 5
| Angle θ (°) | Range of expansion rate (%) | Capability retention (%) | |
| Embodiment 5-1 | 3 | 99.8 | 85.5 |
| Embodiment 5-2 | 5 | 98 | 87.1 |
| Embodiment 5-3 | 15 | 93 | 89.2 |
| Embodiment 5-4 | 30 | 88 | 91.2 |
| Embodiment 5-5 | 45 | 86 | 92.1 |
| Embodiment 5-6 | 60 | 80 | 90.5 |
| Embodiment 5-7 | 70 | 77 | 85.3 |
| Comparative example 5-1 | 0 | 100 | 85.2 |
Shown in table 5 and Figure 10 and 20; In embodiment 5-1 to 5-7; Primary particle 123 tilts from the alignment the same side perpendicular to negative electrode collector 12A with offspring 121, and in comparative example 5-1, primary particle 123 and offspring 121 are almost perpendicular to negative electrode collector.In addition, 5-1 compares with comparative example, and in embodiment 5-1 to 5-7, the range of expansion rate can be littler, and can improve capability retention.That is, find when elementary particle 123 and offspring 121 when the same side tilts, can improve battery behavior such as cycle characteristics, and can reduce the coefficient of expansion of device.
In addition, such trend is arranged: when the angle θ of elementary particle 123 and offspring 121 was bigger, capability retention was improved to maximum, descends then.That is, find primary particle 123 and offspring 121, more preferably with the angle tilt of 15 °-60 ° (comprising end points) preferably from perpendicular to the line of negative electrode collector 12A angle with 5 °-60 ° (comprising end points).
Although reference implementation mode and embodiment have described the present invention, the invention is not restricted to these execution modes and embodiment, and can carry out various improvement.For example, in above-mentioned execution mode and the foregoing description, the situation of the electrolyte solution or the so-called gel electrolyte that wherein are used for liquid electrolyte has been described; But, can use any other electrolyte.As electrolyte, enumerate the mixture of solid electrolyte, solid electrolyte and electrolyte solution or the mixture of solid electrolyte and gel electrolyte with ionic conductance.
As solid electrolyte, for example, can use through electrolytic salt being dispersed in HMW solid electrolyte that forms in the high-molecular weight compounds with ionic conductance or the inorganic solid electrolyte of processing by ionic conducting glass or ionic crystals.High-molecular weight compounds as the HMW solid electrolyte; For example, can use ether-based high molecular to quantize compound such as PEO or comprise that crosslinked, ester-based high molecular of PEO quantize compound such as polymethacrylates or acrylate-based high-molecular weight compounds, its mixture or its copolymer.In addition, as inorganic solid electrolyte, can use the inorganic solid electrolyte that comprises lithium nitride, lithium phosphate etc.
In addition, in above-mentioned execution mode and the foregoing description, the present invention has been described with reference to Coin shape secondary cell and screw winding laminated-type secondary cell; Yet the present invention can be applied to have the secondary cell of any other shape such as column type, prismatic, button type, slim, large-scale or laminated-type in an identical manner.In addition, the present invention not only can be applicable to secondary cell, also can be applicable to primary cell.
It will be understood by those of skill in the art that in the scope of accompanying claims or its equivalent, depend on designing requirement and other factors, can carry out various improvement, combination, make up again and change.
Claims (5)
1. battery comprises:
Anodal;
Negative pole; With
Electrolyte,
Wherein this negative pole comprises the anode active material layer that sticks on the negative electrode collector, and this anode active material layer comprises silicon (Si) element,
This anode active material layer comprises through a plurality of primary particles assembles a plurality of offsprings that form,
The spacing of in 100 μ m * 70 mu m ranges in the part anode active material layer at least, drawing therein is that the average of the offspring of every line is 5-11, and comprises end points under the situation of the long line of eight the 100 μ m of 10 μ m, and
The average of the primary particle of each offspring is 20 or more on line.
2. the battery of claim 1, wherein
In 10 continuous quadratic particles, perpendicular to the quantity of the offspring longer of the length on the direction of thickness direction than the length on the thickness direction than being 50% or more.
3. the battery of claim 1, wherein
40 chargings therein are under the situation of reference charging and discharge with discharge cycles, and the thickness of the anode active material layer when repeating reference charging and the discharge of discharge back be when discharging in the reference charging with before discharging 1.7 times of thickness or littler.
4. the battery of claim 1, wherein
Before lithium (Li) is inserted in the negative active core-shell material in initial charge and discharge.
5. the battery of claim 4, wherein
The electro-chemical activity lithium remains in the anode active material layer after discharge.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004341181A JP4240312B2 (en) | 2004-11-25 | 2004-11-25 | battery |
| JP2004341182A JP4232735B2 (en) | 2004-11-25 | 2004-11-25 | Secondary battery |
| JP341181/04 | 2004-11-25 | ||
| JP341182/04 | 2004-11-25 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101268865A Division CN100470918C (en) | 2004-11-25 | 2005-11-25 | Battery and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101453034A CN101453034A (en) | 2009-06-10 |
| CN101453034B true CN101453034B (en) | 2012-03-21 |
Family
ID=36634006
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101268865A Expired - Fee Related CN100470918C (en) | 2004-11-25 | 2005-11-25 | Battery and manufacturing method thereof |
| CN2008101843409A Expired - Fee Related CN101453034B (en) | 2004-11-25 | 2005-11-25 | Battery and method of manufacturing the same |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101268865A Expired - Fee Related CN100470918C (en) | 2004-11-25 | 2005-11-25 | Battery and manufacturing method thereof |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4240312B2 (en) |
| CN (2) | CN100470918C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008192608A (en) * | 2007-01-11 | 2008-08-21 | Matsushita Electric Ind Co Ltd | Lithium secondary battery |
| JP4525742B2 (en) * | 2007-01-30 | 2010-08-18 | ソニー株式会社 | Negative electrode for lithium ion secondary battery and lithium ion secondary battery |
| US20090317726A1 (en) | 2008-04-08 | 2009-12-24 | Sony Corporation | Anode and secondary battery |
| WO2009125620A1 (en) * | 2008-04-08 | 2009-10-15 | 株式会社村田製作所 | Capacitor and method for manufacturing the same |
| WO2023223581A1 (en) * | 2022-05-16 | 2023-11-23 | パナソニックＩｐマネジメント株式会社 | Battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4748970B2 (en) * | 2003-11-27 | 2011-08-17 | パナソニック株式会社 | Energy device and manufacturing method thereof |
-
2004
- 2004-11-25 JP JP2004341181A patent/JP4240312B2/en not_active Expired - Fee Related
-
2005
- 2005-11-25 CN CNB2005101268865A patent/CN100470918C/en not_active Expired - Fee Related
- 2005-11-25 CN CN2008101843409A patent/CN101453034B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006155957A (en) | 2006-06-15 |
| CN100470918C (en) | 2009-03-18 |
| JP4240312B2 (en) | 2009-03-18 |
| CN1780042A (en) | 2006-05-31 |
| CN101453034A (en) | 2009-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3469648B1 (en) | High energy density, high power density, high capacity, and room temperature capable "anode-free" rechargeable batteries | |
| CN1874032B (en) | Cathode for secondary battery, secondary battery, and method of manufacturing cathode for secondary battery | |
| US7459236B2 (en) | Battery | |
| US7700235B2 (en) | Battery and method of manufacturing the same | |
| US8048563B2 (en) | Anode, battery, and methods of manufacturing them | |
| CN100539257C (en) | Secondary battery cathode and the manufacture method of using its secondary cell and negative pole | |
| CN100470896C (en) | Anode and battery | |
| CN100570929C (en) | The battery of anode and this anode of employing | |
| US20070111103A1 (en) | Current collector, anode, and battery | |
| EP2685531B1 (en) | Negative electrode active material for electrical devices | |
| US7494743B2 (en) | Anode and battery | |
| CN101060170B (en) | Anode and battery | |
| US20090104515A1 (en) | Lithium secondary battery | |
| EP2717357B1 (en) | Negative electrode active material for electrical device, negative electrode for electrical device and electrical device | |
| EP2717358B1 (en) | Negative electrode active material for electrical devices | |
| KR20070077126A (en) | Negative electrode for lithium secondary battery and lithium secondary battery using the negative electrode | |
| KR20060066756A (en) | Electrode for lithium secondary cell and lithium secondary cell | |
| US20050079421A1 (en) | Anode and battery | |
| US7226700B2 (en) | Anode and battery using the same | |
| US9048492B2 (en) | Negative electrode active material for electric device | |
| CN101453034B (en) | Battery and method of manufacturing the same | |
| JP2004171875A (en) | Negative electrode and battery using it | |
| JP2009152182A (en) | Nonaqueous electrolyte secondary battery | |
| US7482095B2 (en) | Anode and battery using the same | |
| US20220384912A1 (en) | Thermally Efficient Pouch Cell Architecture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180417 Address after: Kyoto Japan Patentee after: Murata Manufacturing Co.,Ltd. Address before: Fukushima Patentee before: Murata, Northeast China Effective date of registration: 20180417 Address after: Fukushima Patentee after: Murata, Northeast China Address before: Tokyo, Japan Patentee before: Sony Corp. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120321 Termination date: 20211125 |