CN102812580A - Negative Electrode Active Material, And Secondary Battery, Capacitor And Electricity Storage Device Each Using The Negative Electrode Active Material - Google Patents

Negative Electrode Active Material, And Secondary Battery, Capacitor And Electricity Storage Device Each Using The Negative Electrode Active Material Download PDF

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Publication number
CN102812580A
CN102812580A CN2010800655516A CN201080065551A CN102812580A CN 102812580 A CN102812580 A CN 102812580A CN 2010800655516 A CN2010800655516 A CN 2010800655516A CN 201080065551 A CN201080065551 A CN 201080065551A CN 102812580 A CN102812580 A CN 102812580A
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active material
electrode active
negative electrode
negative
pore
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井户秀和
西内万聪
安藤芽久美
松原智行
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Kobelco Research Institute Inc
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Kobelco Research Institute Inc
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Priority claimed from JP2010095224A external-priority patent/JP5575531B2/en
Priority claimed from JP2010095225A external-priority patent/JP2011228402A/en
Priority claimed from JP2010095223A external-priority patent/JP2011228057A/en
Application filed by Kobelco Research Institute Inc filed Critical Kobelco Research Institute Inc
Publication of CN102812580A publication Critical patent/CN102812580A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • 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
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Abstract

Disclosed are: a negative electrode active material which is capable of prolonging cycle life, while securing a large energy density (large capacity); and a secondary battery, a capacitor and an electricity storage device, each of which uses the negative electrode active material. A negative electrode active material (12) according to one embodiment of the first invention is formed of a lithium-containing aluminum alloy foil body. The foil body is composed of surface portions (12a) respectively provided on the front surface and the back surface, and a base portion (12b). The surface portions (12a) provided on the front surface and the back surface have a three-dimensional network structure and a plurality of fine pores. The surface portions (12a) provided on the front surface and the back surface have a surface aperture ratio of 10-80%.

Description

Negative electrode active material, the secondary cell that has used it and capacitor and electric energy storage device
Technical field
The present invention relates to negative electrode active material, used its secondary cell and capacitor and electric energy storage device.
Background technology
Therefore lithium (Li) ion battery is used as secondary cell and uses owing to have excellent energy density (below be also referred to as " capacity ").As negative electrode active material used in this secondary cell, use the material of the Li that in graphite (C), mixed usually, can Li be doped to C in theory 6Li.But realistic situation is, can only be with the concentration (C that is doped to below it in the practical application 10Li) about.
As secondary battery cathode, studying and having used aluminium (Al)-Li is the electrode of alloy, and with a part of practicability.It is by with Al as main body and comprise the non-aqueous secondary battery that the Al-Li alloy of the Li of 4～12 quality % constitutes and use the Al-Li alloy electrode, it is characterized in that the size of the LiAl compound in the mesh-shape eutectic structure is (with reference to patent documentations 1) below the 10 μ m.
In addition, start from the purpose of the influence of the volumetric expansion of alleviating the metallic negative pole, also studied the electrode that is described below.
For example, studied on the surface or inner tin (Sn) or Sn-nickel (Ni) alloy anode with spherical space.Above-mentioned space constitutes as followsly, that is, the porosity is 10～98%, and the aperture is 0.05～100 μ m, with Li alloying (with reference to patent documentation 2) takes place.
In addition, the known electrode that following formation is arranged promptly, on the collector body of the Ni of the porous matter with the pore below the average diameter 3 μ m or Al system, as the negative electrode active material relevant with cell reaction, maintains Li or zinc (Zn) (with reference to patent documentation 3).
In addition, because capacitor compares the output density height with secondary cell, therefore be regarded as the power storage device that is expected to as regenerative resources such as main power source, accessory power supply or the solar power generation of for example electric automobile or wind power generations.Yet, because therefore the energy density low (that is, capacitance is little) of capacitor has proposed to improve their trial that is described below.
For example, proposed anodal and negative pole folder are immersed in the Li ion mixed capacitor (with reference to patent documentation 4) in the electrolyte across distance piece.Here, contain the imporosity charcoal in the positive pole as active material, contain carbon (C) material that can inhale storage reversiblely, break away from the Li ion in the negative pole as active material, electrolyte is the organic solvent that contains the aprotic of Li salt.
In addition, in Li ion mixed capacitor, particularly known negative electrode active material is arranged is the capacitor (with reference to patent documentation 5) of carbonaceous porousness powder.This carbonaceous porousness powder is the aggregate that the carbon black of the porous matter of the average grain diameter 12～300nm with pore structure is formed with the material with carbon element bonding.In addition, as disclosed carbon (C) material identical materials in positive active material use and the above-mentioned patent documentation 4.
Patent documentation
Patent documentation 1: japanese kokai publication sho 63-51052 communique
Patent documentation 2: TOHKEMY 2006-260886 communique
Patent documentation 3: japanese kokai publication hei 8-321310 communique
Patent documentation 4: TOHKEMY 2007-294539 communique
Patent documentation 5: TOHKEMY 2008-150270 communique
Summary of the invention
The problem that invention will solve
But therefore,, can't alleviate by being accompanied by the stress of the volumetric expansion that discharges and recharges generation due to shrinking because disclosed Al-Li as secondary battery cathode is that alloy is tabular in the above-mentioned patent documentation 1.Thus, will produce the Al-Li that plays a role as negative electrode active material is peeling off of alloy, thereby has the sufficient inadequately problem of life-span that recycles.
In addition, among the disclosed Sn or Sn-Ni alloy anode that has with the space of Li alloying, this space has spherical shape, and separate in above-mentioned patent documentation 2.In this kind structure,, therefore in negative pole, produce the crack easily, thereby have the sufficient inadequately problem of life-span that recycles owing to be accompanied by the space inner wall part that the influence of the volumetric expansion of the Li in the space that charging produces concentrates on Sn or Sn-Ni alloy anode.In addition, in the disclosed manufacturing technology, can't form negative pole in the above-mentioned patent documentation 2 by Al with pore.
In addition, in the above-mentioned patent documentation 3 in the disclosed negative pole, though collector body itself is a porous matter, yet negative electrode active material and non-porous matter.Thus, can't alleviate the influence of the volumetric expansion of negative electrode active material fully, thereby have the sufficient inadequately problem of life-span that recycles.In addition, because negative electrode active material only is made up of Li or Zn, therefore also have the problem of the generation that can't suppress arborescence.
In addition, owing to contain material with carbon element as active material in the disclosed negative pole in the above-mentioned patent documentation 4, therefore in theory also can't obtain C 6The doping of the Li that Li is above can't be expected big capacity.In addition because positive pole is only to utilize anionic absorption to come the mechanism of electric power storage, so capacity compare with negative pole quite little, thereby can't utilize the capacity of negative pole fully.
In addition and since with above-mentioned patent documentation 4 in disclosed negative pole identical, also be to contain material with carbon element in the disclosed negative pole in the above-mentioned patent documentation 5 as active material, therefore in theory also can't obtain C 6The doping of the Li that Li is above can't be expected big capacity.In addition, identical with disclosed positive pole in the above-mentioned patent documentation 4 because positive pole is only to utilize anionic absorption to come the mechanism of electric power storage, thus capacity compare with negative pole quite little, thereby can't utilize the capacity of negative pole fully.
So, the objective of the invention is to, provide and can guarantee big energy density (big capacity) and can prolong the negative electrode active material that recycles the life-span, the secondary cell that has used it and capacitor and electric energy storage device.
In order to realize these purposes; A mode of first invention of the present invention provides a kind of negative electrode active material; It is the negative electrode active material of doing by the paper tinsel system of the aluminium alloy system that contains lithium; At least the skin section of above-mentioned paper tinsel body has three-dimensional mesh-shape skeleton, and has many pores, and the surface opening rate of above-mentioned skin section is 10～80%.
Of the present invention first the invention an other mode a kind of secondary cell is provided, it is characterized in that, comprise negative pole, positive pole with above-mentioned negative electrode active material and be disposed at above-mentioned negative pole and above-mentioned positive pole between ionic conductivity electrolyte.
Of the present invention first the invention an other mode a kind of capacitor is provided, it is characterized in that, comprise negative pole, positive pole with above-mentioned negative electrode active material and be disposed at above-mentioned negative pole and above-mentioned positive pole between ionic conductivity electrolyte.
In addition, in order to realize these purposes, a mode of second invention of the present invention provides a kind of negative-electrode active material for secondary battery, is the negative-electrode active material for secondary battery of being made by the aluminium alloy of porous matter, contains at least a kind in silicon and the tin.
The content of preferred above-mentioned silicon and above-mentioned tin is respectively 0.05～24 atom %, and the content sum of above-mentioned silicon and said tin is below the 30 atom %.
Preferred above-mentioned negative-electrode active material for secondary battery contains the magnesium of 0.02～5 atom %.
An other mode of second invention of the present invention provides a kind of secondary cell; It is characterized in that, comprise negative pole with above-mentioned negative-electrode active material for secondary battery, have contain lithium and can inhale storage, emit lithium positive active material positive pole and be disposed at above-mentioned negative pole and above-mentioned positive pole between ionic conductivity electrolyte.
An other mode of second invention of the present invention provides a kind of capacitor use negative electrode active material, is to use negative electrode active material by the capacitor of the aluminium alloy of porous matter making, contain lithium and be selected from silicon and tin at least a kind.
The content of preferred above-mentioned silicon and above-mentioned tin is respectively 0.05～24 atom %, and the content sum of above-mentioned silicon and above-mentioned tin is below the 30 atom %.
Preferred above-mentioned capacitor contains the magnesium of 0.02～5 atom % with negative electrode active material.
An other mode of second invention of the present invention provides a kind of capacitor, it is characterized in that, comprise have above-mentioned capacitor with negative pole, the positive pole of negative electrode active material and be disposed at above-mentioned negative pole and above-mentioned positive pole between ionic conductivity electrolyte.
In addition; In order to realize these purposes; A mode of the 3rd invention of the present invention provides a kind of negative electrode active material, is the negative electrode active material of being made by the aluminium alloy that contains lithium of the porous matter with pore, it is characterized in that; The opening of above-mentioned pore directly is (but not comprising zero) below the 5 μ m, and the ratio in the opening footpath of the length of above-mentioned pore/above-mentioned pore is more than 10.
The opening of preferred above-mentioned pore directly is 0.1～5 μ m, and the ratio in the opening footpath of the length of above-mentioned pore/above-mentioned pore is 10～100.
Of the present invention the 3rd the invention an other mode a kind of secondary cell is provided, it is characterized in that, comprise negative pole, positive pole with above-mentioned negative electrode active material and be disposed at above-mentioned negative pole and above-mentioned positive pole between ionic conductivity electrolyte.
Of the present invention the 3rd the invention an other mode a kind of capacitor is provided, it is characterized in that, comprise negative pole, positive pole with above-mentioned negative electrode active material and be disposed at above-mentioned negative pole and above-mentioned positive pole between ionic conductivity electrolyte.
In addition; In order to realize these purposes; A mode of the 4th invention of the present invention provides a kind of electric energy storage device; It is characterized in that, comprise negative pole with negative electrode active material of making by the aluminium alloy that contains lithium of porous matter, have the graphite that comprises active carbon be the positive pole of positive active material and be disposed at above-mentioned negative pole and above-mentioned positive pole between ionic conductivity electrolyte.
The invention effect
As stated; According to first invention of the present invention; Because negative electrode active material is done by the paper tinsel system of the aluminium alloy system that contains lithium; At least the skin section of said paper tinsel body has three-dimensional mesh-shape skeleton and has many pores, and the surface opening rate of said skin section is 10～80%, therefore can provide can satisfy high capacity simultaneously and recycle the negative electrode active material of the long lifetime in life-span, the secondary cell that has used it and capacitor.
In addition; According to second invention of the present invention; Because negative-electrode active material for secondary battery is made by the aluminium alloy of porous matter and contained at least a kind in silicon and the tin, therefore can provide and to guarantee jumbo negative electrode active material under the situation that recycles the life-span and to have used its secondary cell not reducing.
In addition; According to second invention of the present invention; Because capacitor is made by the aluminium alloy of porous matter with negative electrode active material and contained lithium and be selected from least a kind in silicon and the tin, so can provide and to guarantee jumbo negative electrode active material under the situation that recycles the life-span and to have used its capacitor not reducing.
In addition; According to the 3rd invention of the present invention; Because negative electrode active material is made by having the aluminium alloy that contains lithium pore, porous matter; The opening of said pore directly is (but not comprising zero) below the 5 μ m, and the ratio in the opening footpath of the length of said pore/said pore is more than 10, therefore can provide and can satisfy high capacity simultaneously and recycle the negative electrode active material of the long lifetime in life-span, the secondary cell that has used it and capacitor.
In addition; According to the 4th invention of the present invention; Because electric energy storage device comprises: have the negative electrode active material of making by the aluminium alloy that contains lithium of porous matter negative pole, have the graphite that comprises active carbon be the positive pole of positive active material and be disposed at said negative pole with said positive pole between ionic conductivity electrolyte, therefore can provide and can not reduce the electric energy storage device of guaranteeing big energy density (capacity greatly) under the situation that recycles the life-span.
Description of drawings
Fig. 1 is the sketch map of synthetic method of an execution mode that is used to explain the negative electrode active material of first invention of the present invention.
Fig. 2 is the local enlarged diagram that utilizes the negative electrode active material of synthetic method formation shown in Figure 1.
Fig. 3 is based on and utilizes from the direction of arrow A that scanning electron microscope is observed, the reference diagram of the photo of the surface state of the skin section of expression negative electrode active material shown in Figure 2.
Fig. 4 is based on and utilizes that scanning electron microscope is observed, the reference diagram of the photo of the profile status of the B-B section of expression negative electrode active material shown in Figure 2.
Fig. 5 is the key diagram of definition of surface opening rate that is used to explain the skin section of negative electrode active material shown in Figure 2.
Fig. 6 is the sketch map of an execution mode that is used to explain the secondary cell of first invention of the present invention.
Fig. 7 is the sketch map of an execution mode that is used to explain the capacitor of first invention of the present invention.
Fig. 8 is the sketch map of an execution mode that is used to explain the secondary cell of second invention of the present invention.
Fig. 9 is the sketch map of an execution mode that is used to explain the capacitor of second invention of the present invention.
Figure 10 is the sketch map of synthetic method of an execution mode that is used to explain the negative electrode active material of the 3rd invention of the present invention.
Figure 11 is the sketch map of an execution mode that is used to explain the secondary cell of the 3rd invention of the present invention.
Figure 12 is the sketch map of an execution mode that is used to explain the capacitor of the 3rd invention of the present invention.
Figure 13 is the sketch map of an execution mode that is used to explain the electric energy storage device of the 4th invention of the present invention.
Wherein, 1,10,30,51,60,80 containers, 2,52, aluminium foil; 3,53 lithium plates, 4,54 electrolyte, 12,32,62,82 negative electrode active materials; The 12a skin section, 12b parent portion, 13,20,33,40,61,63,70,83 collector bodies; 14,21,41,64,71,84 positive active materials, 15,35,42,65,85 infiltrated electrolyte distance piece, 34 positive active material (LiCoO 2)
Embodiment
Below, in reference to accompanying drawing, each mode of the present invention is described.
[first invention]
Below, in reference to Fig. 1～7, first invention of the present invention is described.
(execution mode 1)
Fig. 1 is the sketch map of a mode of synthetic method that is used to the negative electrode active material of the first working of an invention mode 1 of explaining.
Among Fig. 1, symbol 1 expression container, the aluminium foil that symbol 2 expressions are connected with negative side, the lithium plate that symbol 3 expressions are connected with side of the positive electrode, symbol 4 expressions are injected into the electrolyte in the container 1.
(pre-treatment of aluminium foil 2)
Utilize the following pre-treatment condition aluminium foil 2 that is prepared in advance.
As electrolyte, use the aqueous solution that contains 10 quality % hydrochloric acid and 0.1 quality % sulfuric acid.Be controlled to be at aluminium foil in 38 ℃ the above-mentioned electrolyte with 60Hz, current density 180mA/cm purity 99.9%, thick 110 μ m 2After carrying out 500 seconds etching, clean with ion exchange water.
As shown in Figure 1, above-mentioned aluminium foil 2 and the lithium plate 3 that carried out pre-treatment in advance is immersed in the electrolyte 4, be connected respectively and stand facing each other with negative side, side of the positive electrode.And electrolyte 4 is by electrolyte (LiPF 6) and organic solvent (ethylene carbonate (EC): diethyl carbonate (DEC)=1: 1) constitute, concentration is the mixed solution of 1mol/l.Through under this state, being that 25mV is (with respect to Li/Li with the control of Electric potentials of aluminium foil 2 +), 50 ℃ of electrolysis and alloying, just can obtain the negative electrode active material 12 that the aluminium alloy foliation body by containing lithium of the test No.1A～9A shown in the below table 1 constitutes (with reference to Fig. 2～Fig. 7).
[table 1]
Figure BDA00002153499100081
Fig. 2 is the local enlarged diagram that utilizes the negative electrode active material 12 of synthetic method formation shown in Figure 1.Show among Fig. 2 that negative electrode active material 12 is made up of skin section 12a and the 12b of parent portion.This skin section 12a is the structure (demonstrating so-called spongelike structure) that has three-dimensional mesh-shape skeleton and have many pores.The opening footpath D of this pore is 0.5 μ m～2 μ m.In addition, said here pore is the general name in some holes of comprising that pre-treatment condition because of above-mentioned aluminium foil 2 etc. produces.
Fig. 3 is based on the reference diagram of photo of face surface state of the skin section 12a of expression negative electrode active material 12 shown in Figure 2, and said surface state is observed the surface by utilizing scanning electron microscope of the skin section 12a of negative electrode active material shown in Figure 2 12 and obtained from the direction of arrow A.
Fig. 4 is based on the reference diagram of photo of profile status of the B-B section of expression negative electrode active material 12 shown in Figure 2, and the B-B section that said profile status utilizes scanning electron microscope to observe negative electrode active material 12 shown in Figure 2 obtains.According to Fig. 4, the average thickness of skin section 12a is about 5 μ m.And with reference to the purpose of the application's invention, the average thickness of this skin section 12a is preferably 1 μ m～50 μ m.In addition, though with regard to Fig. 2～Fig. 4, the skin section 12a of the surface of anticathode active material 12 (one side side) has spongelike structure and is illustrated, yet also has the skin section 12a of spongelike structure at the back side of negative electrode active material 12 (another side side).
As stated, skin section 12a has many pores, and the opening of this pore footpath D is preferably 0.1～5 μ m.This be because, if the opening of pore footpath D surpasses 5 μ m, then the surface area of negative electrode active material 12 reduces and capacity is reduced, if less than 0.1 μ m, the immersion of electrolyte in above-mentioned pore of stating after the then difficulty that will become.But the section shape of pore is not defined as circle.
In addition, utilize above-mentioned scanning electron microscope to observe the surface of skin section 12a and the proterties of section, determine the surface opening rate.The definition list of this aperture opening ratio is shown among Fig. 5.In this definition, the opening footpath D of pore is an average diameter, and the distance L between pore is an average length.The result distinguishes according to said determination, and the surface opening rate of skin section 12a was preferably for 10～80% (with reference to above-mentioned table 1).Can think, when the charging of secondary cell, produce volumetric expansion because of the lithium contents in the negative electrode active material 12 increase, and if the surface opening rate less than 10%, then just abundant inadequately to the alleviation of the stress that causes by this volumetric expansion.Can think in addition,, then inadequately fully (state table 2, table 3 after the details reference) as the mechanical strength of negative electrode active material 12 if the surface opening rate surpasses 80%.
In the negative electrode active material 12 of the test No.1A～9A shown in the above-mentioned table 1 which to be suitable for secondary cell purposes and capacitor purposes for, will after state in the execution mode 2,3 and detail.And, though in this execution mode, be that example is illustrated with the aluminium foil 2 of thick 110 μ m, yet not necessarily be defined in this, also can use the aluminium foil of thick about 5 μ m～200 μ m.In addition, though in this execution mode, aluminium alloy is illustrated by the example that Al and Li constitute in fact, yet not necessarily is defined in this.Also can use the aluminium alloy of elements such as except that Li, containing Mg, Zn.And, also can contain the following Si of 0.05 atom (at) %, Fe, Cu, Mn, Mg, Zn, Ti etc. as unavoidable impurities in the aluminium alloy of first invention.In addition, though in this execution mode,, the aluminium foil 2 with purity 99.9% is connected with negative side and is that 25mV is (with respect to Li/Li with control of Electric potentials as the condition of synthetic negative electrode active material 12 +), electrolysis and the example of alloying is illustrated in 50 ℃ electrolyte, yet not necessarily be defined in this.Aluminium can be through electrolysis and Li alloying.
(execution mode 2)
Fig. 6 is the sketch map of a mode that is used to the secondary cell of the first working of an invention mode 2 of explaining.
Among Fig. 6, symbol 10 expression containers, symbol 12 expressions utilize the synthetic negative electrode active material that obtain identical with above-mentioned execution mode 1, the collector body of symbol 13 expression aluminums, symbol 14 is represented positive active materials.The distance piece of electrolyte 4 infiltrations that the electrolyte that uses in symbol 15 expression quilts and above-mentioned execution mode 1 synthetic in addition, is identical.Distance piece 15 be by negative electrode active material 12 and through coating on collector body 13 dry be provided with have a MnO 2The formation of positive active material 14 clampings.Adapt with the negative electrode active material 12 of the test No.1A～9A shown in the above-mentioned table 1 of above-mentioned execution mode 1, the secondary cell that so constitutes is made as test No.1A～9A, and is shown in the below table 2.
[table 2]
Figure BDA00002153499100111
Determine the voltage of the secondary cell that constitutes as illustrated in fig. 6.Then, carry out the cyclic test (depth of discharge 20%) of these secondary cells, the period of the time point that final discharging voltage is begun to reduce sharp is made as and recycles the life-span.In addition, observe the surface of each negative electrode active material 12, confirm to have or not arborescence to generate.Its result is shown in the above-mentioned table 2.
Shown in above-mentioned table 2, in test No.1A～9A, all do not see the generation of arborescence.In addition, the life-span that recycles of test No.1A～7A is 680～1500, satisfies the set-point (more than 600) as target.Can think this because; Because the skin section 12a of negative electrode active material 12 of test No.1A～7A has three-dimensional mesh-shape skeleton and many pores (having spongelike structure), therefore realized the alleviation (having absorbed influence) of the stress that the volumetric expansion to by charging the time causes.On the other hand, the life-span that recycles of test No.8A, 9A is respectively 120,130, is lower than set-point.Can think this because; If the surface opening rate of skin section 12a is less than 10% as test No.8A; Then skin section 12a has not had spongelike structure, the alleviation of the stress that can't realize the volumetric expansion by when charging is caused (can't inhalation effects).Can think in addition because if the surface opening rate surpasses 80% as test No.9A, then the mechanical strength of negative electrode active material 12 is just abundant inadequately, can't satisfy the given life-span that recycles.So the surface opening rate is preferably 10～80%.
Can know that according to these results the secondary cell that satisfies as the given performance of target is test No.1A～7A.So the negative electrode active material 12 that is fit to this secondary cell is the test No.1A～7A shown in the above-mentioned table 1.Can know like this; The negative electrode active material that the negative electrode active material 12 of test No.1A～7A shown in the above-mentioned table 1 of above-mentioned execution mode 1 is used as secondary cell; Do not have the generation of arborescence, and given play to obvious effects for the long lifetime that recycles the life-span.
(execution mode 3)
Fig. 7 is the sketch map of a mode that is used to the capacitor of the first working of an invention mode 3 of explaining.
Among Fig. 7, the collector body of symbol 20 expression aluminums, symbol 21 expression positive active materials, the infiltrated distance piece of electrolyte of symbol 22 expressions.In this execution mode,, omit detailed explanation for using identical numbering with the identical key element of formation of execution mode 1,2.
Distance piece 22 be by negative electrode active material 12 and through coating on collector body 20 dry be provided with have an active carbon (BET specific area: 800～1300m 2/ g) the structure of positive active material 21 clampings.Electrolyte to distance piece 22 infiltrations is by electrolyte (LiBF 4) and the concentration that constitutes of organic solvent { ethylene carbonate (EC): the mixed solution of methyl ethyl carbonate (EMC)=1: 1 } be the electrolyte of 1.5mol/l.Adapt with the negative electrode active material 12 of the test No.1A～9A shown in the above-mentioned table 1, the capacitor that so constitutes is made as test No.1A～9A, be shown in the below table 3.In addition, in order to compare, (the BET specific area is 50m will to have used Delanium as negative electrode active material 12 2/ g) capacitor is made as test No.10A.
[table 3]
Figure BDA00002153499100131
These capacitors are charged to given voltage with constant current and constant voltage in 25 ℃ thermostat, to 1.0V, the period of the time point that static capacity is begun to reduce sharp is made as and recycles the life-span with constant current discharge.In addition, observe the surface of negative electrode active material 12, confirm to have or not arborescence to generate.
Shown in above-mentioned table 3, in test any among No.1A～10A, all do not see the generation of arborescence.In addition,, satisfy set-point (more than 600), yet the life-span that recycles of test No.8A, 9A is 200,100, is lower than set-point respectively as target though the life-span that recycles of test No.1A～7A is 600～1200.Can think this by with above-mentioned execution mode 2 in the identical reason of explanation cause.In addition, the life-span that recycles of test No.10A is 500, is lower than the set-point (more than 600) as target.Can think this because, cause the splitting that has used the negative pole of Delanium as negative electrode active material owing to be accompanied by the volume contraction expansion that the discrepancy of the Li ion when discharging and recharging produces.
In addition, with the capacitor that constitutes as illustrated in fig. 7 in 25 ℃ thermostat with constant current discharge to 1.0V.After this, will carry out time integral to the product of the voltage V in when discharge and electric current I and the discharge energy conduct equal 1/2CV 2Value, obtain the static capacity C (F/g) of the per unit weight of negative electrode active material 12.Its result is shown in the above-mentioned table 3.
Shown in above-mentioned table 3, any static capacity C (more than the 300F/g) who all satisfies as the given per unit weight of target of test No.1A～10A.
Can know that according to these results the formation that satisfies as the capacitor of the given performance of target is test No.1A～7A.That is, with coming to the same thing of the secondary cell of above-mentioned execution mode 2, the negative electrode active material 12 that is fit to capacitor is test No.1A～7A.Can know like this; The negative electrode active material that the negative electrode active material 12 of test No.1A～7A shown in the above-mentioned table 1 of above-mentioned execution mode 1 is used as capacitor; Can realize high capacity and not have the generation of arborescence, and give play to obvious effects for the long lifetime that recycles the life-span.The content of Li in the negative electrode active material 12 is preferably 1at%～70at%.This be because, if the content of Li less than 1at%, then energy density diminishes, if the content of Li surpasses 70at%, then is easy to generate arborescence as stated.And, in this execution mode, owing to be prerequisite with bigger energy density (that is, being more than the 300F/g) as the static capacity C of the given per unit weight of target, so the content of the Li in the negative electrode active material 12 10at%～70at% more preferably.
And, though in the first working of an invention mode 2,3, the formation that does not have collector body is set with respect to negative electrode active material 12 in addition is illustrated, yet not necessarily is defined in this.For example, also can through with negative electrode active material 12 folder across conductive paste and collector body made of copper lightly crimping constitute negative pole, wait collector body to be set in addition through operation like this with respect to negative electrode active material 12.
[second invention]
Below, in reference to Fig. 8,9, second invention of the present invention is described.
(negative-electrode active material for secondary battery and capacitor are with the preparation of negative electrode active material)
(pre-treatment of aluminium foil)
1), uses the aqueous solution that contains 5.5 quality % hydrochloric acid, 1.5 quality % phosphoric acid and 0.5 quality % nitric acid, 2.0 quality % aluminium chloride as electrolyte.To have given composition aluminium foils (do not contain Li, details are formed with reference to below table 4, table 5), thick 110 μ m in being controlled to be 18 ℃ above-mentioned electrolyte with 10Hz, current density 120mA/cm 2Triangular wave alternating current etching after 10 seconds～27 minutes, clean with ion exchange water.
2) then, these aluminium foils, are cleaned with ion exchange water after 2 minutes～3 minutes with 60 ℃ of dippings in 5.0 quality % aqueous sulfuric acids.
Utilize these operations, accomplish negative electrode active material 32 (with reference to Fig. 8) shown in the test No.1B～5B of below table 4 and 7B～9B, that need not contain lithium (Li).In this negative electrode active material 32, have and state the such many pores of bright details as follows.
(negative-electrode active material for secondary battery and capacitor are synthetic with negative electrode active material)
In the above-mentioned aluminium foil that carried out pre-treatment in advance, contain under the situation of lithium (Li), above-mentioned aluminium foil and the lithium plate that carried out pre-treatment in advance is immersed in the electrolyte, be connected and stand facing each other with negative side, side of the positive electrode respectively.And electrolyte is by electrolyte (LiPF 6) and organic solvent (ethylene carbonate (EC): the concentration that diethyl carbonate (DEC)=1: 1) constitutes is the mixed solution of 1mol/l.Through under this state, being that 25mV is (with respect to Li/Li with the control of Electric potentials of said aluminium foil +) 50 ℃ of following electrolysis and alloying, obtain shown in the test No.6B of below table 4 as shown in the test No.11B～21B of the negative electrode active material 32 (with reference to Fig. 8) of negative-electrode active material for secondary battery and below table 5 as the negative electrode active material 32 (with reference to Fig. 9) of capacitor with negative electrode active material.These utilize the synthetic negative electrode active material 32 that obtains to have many pores.In addition, said here pore is the general name in some holes of comprising that pre-treatment condition because of above-mentioned aluminium foil etc. produces.The distribution of pore is roughly even, utilizes the ratio of the shared area of pore in the surface of the above-mentioned synthetic negative electrode active material 32 that obtains to be preferably 10%～80%.In the distribution of this pore, reflect the distribution of the pore of the above-mentioned aluminium foil that carried out pre-treatment in advance.In addition, this has lithium content in the negative electrode active material 32 of porous matter of the pore electric weight can be according to above-mentioned compound experiment the time and calculates (with reference to below table 4, table 5).
[table 4]
Figure BDA00002153499100161
[table 5]
Figure BDA00002153499100171
(formation of negative pole)
Like Fig. 8, shown in Figure 9, negative electrode active material 32 is used as negative pole.
(execution mode 1)
Fig. 8 is the sketch map of a mode that is used to the secondary cell of the second working of an invention mode 1 of explaining.
Among Fig. 8, symbol 30 expression containers, the collector body of symbol 33 expression aluminums, symbol 34 expressions contain lithium and can inhale the LiCoO as positive active material that seasoning goes out lithium 2, symbol 35 expression infiltrated with above-mentioned negative-electrode active material for secondary battery synthetic in the distance piece of the identical electrolyte of the electrolyte that uses.Distance piece 35 is by negative electrode active material 32 with through the dry LiCoO that is provided with of coating on collector body 33 2The formation of 34 clampings.The negative electrode active material of using with the secondary cell of the test No.1B～9B shown in the above-mentioned table 4 32 adapts, and the secondary cell that so constitutes is made as test No.1B～9B, is shown in the table 6.
[table 6]
Figure BDA00002153499100181
Determine the voltage of the secondary cell that constitutes as illustrated in fig. 8.Then, these secondary cells are carried out cyclic test (depth of discharge 20%), the period that capacity is reduced to 80% the time point at initial stage is made as and recycles the life-span.In addition, obtain the initial stage capacity of negative plates, and observe the surface of negative electrode active material 32 and confirm to have or not arborescence to generate.Its result is shown in the above-mentioned table 6.
Shown in above-mentioned table 6, the voltage of test No.1B～9B is 3.5～3.9V, has produced the given voltage as target.In addition, the life-span that recycles of test No.1B～7B, 9B is 970 times～1830 times, satisfies the set-point (more than 600 times) as target.Can think this because in test No.1B～7B, 9B, make volumetric expansion because of the lithium contents in the negative electrode active material 32 increase during charging, yet owing to be porous structure, that therefore spreads all over negative electrode active material 32 internally will influence absorption, alleviation.On the other hand, the life-span that recycles of test No.8B is 320 times, is lower than set-point.Can think because in test No.8B, the content of magnesium (Mg) is many, the cyclicity deterioration this.In addition, test No.4B～6B owing to contain an amount of Mg, so the raising of the mechanical strength of negative electrode active material 32, consider it is favourable from the aspect that recycles the life-span.
In addition; Shown in above-mentioned table 6,, satisfy and to give constant volume (more than the 800mAh/g) as target though the initial stage capacity of negative plates of test No.1B～7B is 810～1350mAh/g; Yet the initial stage capacity of negative plates of test No.8B, 9B is respectively 740,790, is lower than to constant volume.Become big for the initial stage capacity of negative plates of testing No.1B～7B like this, can think to be caused by following reason, that is, with regard to the ability of inhaling the storage lithium, with respect to graphite, aluminium is 2.3 times, and silicon (Si) is 4.4 times, and tin (Sn) is 4.4 times.And the content of silicon and tin is preferably 0.05～24 atom (at) % respectively.In addition, under the situation that contains silicon and tin both sides, add up to content to be preferably below the 30 atom %.This be because, if the content separately of silicon and tin less than 0.05 atom %, the effect of then inhale storing lithium is little.In addition, the content of silicon or tin surpass under the situation of 24 atom % respectively or the total content of silicon and tin above under the situation of 30 atom %, be difficult to make porous matter shape negative electrode active material.
In addition, among test No.1B～9B, do not see the generation of arborescence yet.Can know according to above result, realize not reducing guarantee jumbo negative electrode active material under the situation that recycles the life-span and used it secondary cell aspect, test No.1B～7B is fit to.
(execution mode 2)
Fig. 9 is the sketch map that is used to explain an execution mode of capacitor of the present invention.
Among Fig. 9, the collector body of symbol 40 expression aluminums, symbol 41 expression positive active materials, the infiltrated distance piece of electrolyte of symbol 42 expressions.In this execution mode, use identical numbering, omit detailed explanation for the key element identical with the formation of the second working of an invention mode 1.
Distance piece 42 have the negative electrode active material 32 used by above-mentioned capacitor and through coating on collector body 40 dry be provided with have an active carbon (BET specific area: 800～1300m 2/ g) the formation of positive active material 41 clampings.Electrolyte to distance piece 22 infiltrations is by electrolyte (LiBF 4) and the concentration that constitutes of organic solvent { ethylene carbonate (EC): the mixed solution of methyl ethyl carbonate (EMC)=1: 1 } be the electrolyte of 1.5mol/l.The negative electrode active material of using with the capacitor of the examination No.11B～21B shown in the table 5 32 adapts, and the capacitor that so constitutes is made as test No.11B～21B, is shown in the table 7.
[table 7]
Figure BDA00002153499100201
Determine the voltage of the capacitor that constitutes as illustrated in fig. 9.In addition, with the capacitor that constitutes as illustrated in fig. 9 in 25 ℃ thermostat with constant current discharge to 1.0V.After this, make product to the voltage V in when discharge and electric current I carry out time integral and must discharge energy equal 1/2CV 2, obtain the static capacity C (F/g) of the per unit weight of negative electrode active material 12.Its result is shown in the above-mentioned table 7.
Shown in above-mentioned table 7, the voltage of test No.11B～21B is 3.3～3.8V, has produced the given voltage as target.In addition,, satisfy set-point (more than the 1800F/g), yet the static capacity C of test No.20B, 21B is 1740,1790, is lower than set-point respectively as target though the static capacity C of test No.11B～19B is 1840～2450F/g.Become big for the static capacity C that tests No.11B～19B like this, can think because, with regard to the ability of inhaling the storage lithium, with respect to graphite, aluminium is 2.3 times, silicon (Si) is 4.4 times, tin (Sn) is 4.4 times.And the content of silicon and tin is preferably 0.05～24 atom (at) % respectively.In addition, under the situation that contains silicon and tin both sides, add up to content to be preferably below the 30 atom %.This be because, if the content separately of silicon and tin less than 0.05 atom %, the effect of then inhale storing lithium is little.In addition, the content of silicon or tin surpass under the situation of 24 atom % respectively or the total content of silicon and tin above under the situation of 30 atom %, be difficult to make porous matter shape negative electrode active material.
Then, these capacitors are charged to given voltage with the constant current constant voltage in 25 ℃ thermostat, to 1.0V, the period that static capacity is reduced to 70% the time point at initial stage is made as and recycles the life-span with constant current discharge.In addition, observe the surface of negative electrode active material 12, confirm to have or not arborescence to generate.Its result is shown in the above-mentioned table 7.
Shown in above-mentioned table 7, the life-span that recycles of test No.11B～19B, 21B is 14000 times～110000 times, satisfies the set-point (more than 10000 times) as target.Can think this because; Among test No.11B～19B, the 21B; Make volumetric expansion in when charging because of the lithium content negative electrode active material 32 in increases, yet owing to be porous structure, that therefore can spread all over negative electrode active material 32 internally will influence absorption, alleviation.But the life-span that recycles of test No.20B is 3000 times, is lower than set-point.Can think because because Mg content is many among the test No.20B, so the influence of volumetric expansion is alleviated abundant inadequately this.In addition, test No.14B～18B is owing to contain an amount of Mg, and the mechanical strength of negative electrode active material 32 improves, and therefore when realizing high capacity, also is favourable satisfying higher recycling aspect the life-span.
In addition, among test No.11B～21B, do not see the generation of arborescence yet.Comprehensive above result can know, to guarantee jumbo negative electrode active material under the situation that recycles the life-span and has used its capacitor in order to be implemented in not reduce, and is fit to adopt test No.11B～19B.
And, though in this execution mode, be that example is illustrated with the aluminium foil of thick 110 μ m, yet not necessarily be defined in this, can use the aluminium foil of thick about 5 μ m～200 μ m.In addition, in this execution mode, shown in above-mentioned table 4, the negative electrode active material as secondary cell is used is illustrated using the example that suitably contains the alloy of Si, Sn, Mg as the center with Al.But the negative electrode active material that secondary cell is used also can contain the following Fe of 0.05at%, Cu, Mn, Zn, Ti etc. as unavoidable impurities.In addition, shown in above-mentioned table 4, in this execution mode, to will being that the example that negative electrode active material that alloy that Si, Sn, Mg are suitably contained in the center is used as capacitor uses is illustrated with Al and Li.But the negative electrode active material that capacitor is used also can contain the following Fe of 0.05at%, Cu, Mn, Zn, Ti etc. as unavoidable impurities.In addition, the content of the Li in the negative electrode active material used of capacitor is preferably 5at%～70at%.This be because, if the content of Li less than 5at%, then energy density diminishes, if the content of Li surpasses 70at%, then is easy to generate the volume arborescence of electrode.And the content of Li is 30at%～65at% more preferably.
And, though in the second working of an invention mode 1,2, the formation that does not have collector body is set with respect to negative electrode active material 32 in addition is illustrated, yet not necessarily is defined in this.For example, also can constitute negative pole, wait collector body to be set in addition with respect to negative electrode active material 32 through operation like this through negative electrode active material 32 folders are crimped on the collector body made of copper across conductive paste lightly.
[the 3rd invention]
Below, in reference to Figure 10～12, to of the present invention the 3rd the invention an execution mode describe.
(execution mode 1)
Figure 10 is the sketch map of synthetic method that is used to explain an execution mode of negative electrode active material of the present invention.Among Figure 10, symbol 51 is containers, and symbol 52 is the aluminium foils that are connected with negative side, and symbol 53 is the lithium plates that are connected with side of the positive electrode, and symbol 54 is the electrolyte that is injected in the container 51.
(pre-treatment of aluminium foil 52)
Utilize the following pre-treatment condition aluminium foil 52 that is prepared in advance.
1), uses the aqueous solution that contains 5.5 quality % hydrochloric acid, 1.5 quality % phosphoric acid and 0.5 quality % nitric acid, 2.0 quality % aluminium chloride as electrolyte.Be controlled to be at aluminium foil 52 in 18 ℃ the above-mentioned electrolyte, with 10Hz, current density 120mA/cm with purity 99.9%, thick 110 μ m 2Triangular wave alternating current etching after 10 seconds～27 minutes, clean with ion exchange water.
2) then, these aluminium foils 52, are being cleaned with ion exchange water after 2 minutes～3 minutes with 60 ℃ of dippings in 5.0 quality % aqueous sulfuric acids.
Among Figure 10, above-mentioned aluminium foil 52 and the lithium plate 53 that carried out pre-treatment in advance is immersed in the electrolyte 54, is connected respectively and stands facing each other with negative side, side of the positive electrode.And electrolyte 54 is by electrolyte (LiPF 6), organic solvent (ethylene carbonate (EC): diethyl carbonate (DEC)=1: 1) constitute, concentration is the mixed solution of 1mol/l.Through under this state, being that 25mV is (with respect to Li/Li with the control of Electric potentials of aluminium foil 52 +) and 50 ℃ of following electrolysis and alloying, obtain the negative electrode active material 62 (with reference to Figure 11, Figure 12) of the test No.1C～10C shown in the below table 8.Utilize this synthetic aluminium alloy that contains lithium that obtains to have many pores.Here the said aluminium alloy that contains lithium is also to comprise because of synthesis condition etc. containing some not general names of the aluminium alloy that contains lithium of alloy portion at central part.In addition, said here pore is the general name in some holes of comprising that also pre-treatment condition because of aluminium foil 52 etc. produces.In addition, the length of the opening of the pore shown in the below table 8 footpath and pore is defined as followsly.That is, because the section shape of pore is not necessarily circle, therefore the opening of said pore directly is meant the maximum cross section length of the section of pore here.In addition, because also punctulate degree of depth situation about deforming, therefore the length of said pore is meant the maximum length of pore here.In addition, the distribution of pore is even haply, utilizes the ratio of the shared area of pore in the surface of the above-mentioned synthetic negative electrode active material 62 that obtains to be preferably 30%～80%.In the distribution of this pore, reflect the distribution of the pore of the above-mentioned aluminium foil 52 that carried out pre-treatment in advance.
[table 8]
Figure BDA00002153499100231
In addition; Utilize scanning electron microscope to observe the surface of the negative electrode active material 62 that utilizes the above-mentioned synthetic test No.1C～10C that obtains and the proterties of section; Determine the opening footpath of pore and the length of pore, calculate the ratio in opening footpath of the length/pore of pore.Its result is shown in the above-mentioned table 8.Electric weight during in addition, according to above-mentioned compound experiment is calculated the lithium content (with reference to above-mentioned table 8) in the negative electrode active material 62.
Shown in above-mentioned table 8, utilizing the opening of the pore of the negative electrode active material 62 that synthesizes the test No.1C～10C that obtains directly is 0.05 μ m～7 μ m, and the ratio in the opening footpath of the length/pore of pore is 7～103.In addition, pore roughly disperses on the surface of negative electrode active material 62 equably, and the shared area ratio of the pore in this surface is 30%～80% scope.For in the negative electrode active material 62 of this test No.1C～10C which be suitable for secondary cell purposes and capacitor purposes will after state in the execution mode 2,3 and detail.And, though in this execution mode, the situation of the aluminium foil 52 that uses thick 110 μ m is illustrated, yet not necessarily is defined in this, also can use the aluminium foil of thick about 5 μ m～200 μ m.In addition, though in this execution mode, aluminium alloy is illustrated by the example that Al and Li constitute in fact, yet not necessarily is defined in this, also can use the aluminium alloy of elements such as except that Li, containing Mg, Zn.And in the 3rd invention, aluminium alloy also can contain Si below 0.05%, Fe, Cu, Mn, Mg, Zn, Ti etc. as unavoidable impurities.In addition, though in this execution mode,, the aluminium foil 52 with purity 99.9% is connected with negative side, is that 25mV is (with respect to Li/Li with control of Electric potentials as the condition of synthetic negative electrode active material 62 +), electrolysis and the example of alloying is illustrated in 50 ℃ electrolyte, yet not necessarily be defined in this.For example, after utilizing etching, through (0.3V is (with respect to Li/Li with constant potential in containing the aprotic electrolyte of Li ion with the fine aluminium porous +) below) carry out catholyte, also can with the Li alloying.
(execution mode 2)
Figure 11 is the sketch map of a mode that is used to the secondary cell of the 3rd working of an invention mode 2 of explaining.
Among Figure 11, symbol 60 expression containers, symbol 61 expressions collector body made of copper, symbol 62 expressions utilize the synthetic negative electrode active material that obtains described in the above-mentioned execution mode 1, the collector body of symbol 63 expression aluminums, symbol 64 expression positive active materials.The distance piece of electrolyte 54 infiltrations that in addition, symbol 65 expression quilts are identical with the synthetic middle electrolyte that uses described in the above-mentioned execution mode 1.Distance piece 65 by folder across conductive paste be crimped on lightly on the collector body 61 negative electrode active material 62 and through coating on collector body 63 dry be provided with have a MnO 2Positive active material 64 clampings.Adapt with the negative electrode active material 62 that is shown in the test No.1C～10C in the table 8 in the above-mentioned execution mode 1, the secondary cell that so constitutes is made as test No.1C～10C, be shown in the below table 9.
[table 9]
Figure BDA00002153499100251
Determine the voltage of the secondary cell that constitutes as illustrated in fig. 11.Then, carry out cyclic test (depth of discharge 20%), the period of the time point that final discharging voltage is begun to reduce sharp is made as and recycles the life-span.In addition, observe the surface of negative electrode active material 62, confirm to have or not arborescence to generate.Its result is shown in the above-mentioned table 9.
Shown in above-mentioned table 9, the voltage of test No.1C～10C is 2.7～3.7V, has produced the given voltage as target.In addition, satisfy set-point (more than 600) though test the life-span that recycles of No.1C～7C, yet the life-span that recycles of test No.8C～10C is 210, is lower than set-point as target.Can think this because; In test No.1C～7C; When charging, increase because of the lithium content in the negative electrode active material 62; Volume expands, yet because the aspect ratio of the pore in the negative electrode active material 62 big (ratio in the opening footpath of the length/pore of pore is more than 10), therefore spreading all over internally will influence absorption, alleviation as the negative electrode active material 62 of porous structure.On the other hand, among test No.8C～10C, the ratio in the opening footpath of the length/pore of pore is less than 10, thereby can think, the influence alleviation of volumetric expansion is abundant inadequately.In addition, even the ratio in the opening footpath of the length/pore of pore surpasses 100, effect also not too can increase.So the ratio in the opening footpath of the length/pore of pore is preferably 10～100.
In addition, consider that be not only the ratio in opening footpath of the length/pore of pore, the opening of pore absolute value directly also is restricted from the viewpoint of energy density.If the opening of pore directly surpasses 5 μ m, then the surface area of negative electrode active material 62 reduces and energy density is reduced.In addition, if the opening of pore footpath less than 0.1 μ m, then the immersion of electrolyte in pore is just abundant inadequately.So the opening of pore directly is preferably 0.1～5 μ m.
In addition, though in test No.1C～9C, do not see the generation of arborescence, in test No.10C, see the generation of arborescence.According to these results, the formation that satisfies as the secondary cell of the given performance of target is test No.1C～7C.So the negative electrode active material 62 that is fit to this secondary cell is the test No.1C～7C shown in the above-mentioned table 8 of above-mentioned execution mode 1.Can know like this; The negative electrode active material that the negative electrode active material 62 of test No.1C～7C shown in the above-mentioned table 8 of above-mentioned execution mode 1 is used as secondary cell does not have the generation of arborescence, and has given play to obvious effects for the long lifetime that recycles the life-span.
(execution mode 3)
Figure 12 is the sketch map of a mode that is used to the capacitor of the 3rd working of an invention mode 3 of explaining.
Among Figure 12, symbol 70 is collector bodies of aluminum, and symbol 71 is positive active materials, and symbol 72 is the distance pieces of electrolyte of having infiltrated.In this execution mode, use identical numbering, omit detailed explanation for the key element identical with the formation of the 3rd working of an invention mode 1,2.
Distance piece 72 by folder across conductive paste be crimped on lightly negative electrode active material 62 on the collector body 61, through coating on collector body 70 dry be provided with have an active carbon (BET specific area: 800～1300m 2/ g) positive active material 71 clampings.Electrolyte to distance piece 72 infiltrations is by electrolyte (LiBF 4) and the concentration that constitutes of organic solvent { ethylene carbonate (EC): the mixed solution of methyl ethyl carbonate (EMC)=1: 1 } be the electrolyte of 1.5mol/l.Adapt with the negative electrode active material 62 of the test No.1C～10C shown in the above-mentioned table 8 of above-mentioned execution mode 1, test No.1C～10C being made as shown in capacitor that so constitutes such as the below table 10.In addition, in order to compare, in test No.11C,, use Delanium (BET specific area 50m as negative electrode active material 2/ g).
[table 10]
With the capacitor that constitutes as illustrated in fig. 12 in 25 ℃ thermostat with constant current discharge to 1.0V.After this, will carry out time integral to the product of the voltage V in when discharge and electric current I and the discharge energy conduct equal 1/2CV 2Value, obtain the static capacity C (F/g) of the per unit weight of negative electrode active material 62.Its result is shown in the above-mentioned table 10.
Shown in above-mentioned table 10, test No.1C～11C satisfies the static capacity C (more than the 300F/g) as the given per unit weight of target.
Then, these capacitors are charged to given voltage with the constant current constant voltage in 25 ℃ thermostat after, to 1.0V, the period of the time point that static capacity is begun to reduce sharp is made as and recycles the life-span with constant current discharge.In addition, observe the surface of negative electrode active material 62, confirm to have or not arborescence to generate.Its result is shown in the above-mentioned table 10.
Shown in above-mentioned table 10, satisfy set-point (more than 600) though test the life-span that recycles of No.1C～7C, yet the life-span that recycles of test No.8C～11C is 200～500, is lower than set-point as target.Can think this by with the secondary cell of the 3rd working of an invention mode 2 in the identical reason explained cause.Promptly; In test No.1C～7C; When charging,, the lithium content in the negative electrode active material 62 makes volumetric expansion because of increasing; Yet because the aspect ratio of the pore in the negative electrode active material 62 big (ratio in the opening footpath of the length/pore of pore is more than 10), therefore spread all over porous structure negative electrode active material 62 internally will influence absorption, alleviation.On the other hand, among test No.8C～10C, the ratio in the opening footpath of the length/pore of pore is less than 10, thereby can think, and is abundant inadequately to the influence alleviation of volumetric expansion.In addition, even the ratio in the opening footpath of the length/pore of pore surpasses 100, effect also not too can increase.So the ratio in the opening footpath of the length/pore of pore is preferably 10～100.In addition; The life-span that recycles for test No.11C is lower than below the set-point; Can think because, caused the splitting of Delanium as the negative pole of negative electrode active material use owing to be accompanied by volume contraction and the expansion that the discrepancy of the Li ion when discharging and recharging produces.
In addition, in capacitor, also be based on the identical reason of explaining in the secondary cell with the 3rd working of an invention mode 2; Promptly; Based on the viewpoint of energy density, be not only the ratio in opening footpath of the length/pore of pore, and the absolute value in the opening of pore footpath is restricted also.That is, if the opening of pore directly surpasses 5 μ m, then the surface area of negative electrode active material 62 reduces and energy density is reduced, if less than 0.1 μ m, then the immersion of electrolyte in pore is just abundant inadequately.So the opening of pore directly is preferably 0.1～5 μ m.
In addition, though in test No.1C～9C, 11C, do not see the generation of arborescence, in test No.10C, see the generation of arborescence.According to these results, the formation that satisfies as the capacitor of the given performance of target is test No.1C～7C.That is, the negative electrode active material 62 that is fit to this capacitor also with the coming to the same thing of the secondary cell of above-mentioned execution mode 2, be test No.1C～7C.Can know like this; The negative electrode active material that the negative electrode active material 62 of test No.1C～7C shown in the above-mentioned table 8 of above-mentioned execution mode 1 is used as capacitor can be realized high capacity and not have the generation of arborescence, and give play to obvious effects for the long lifetime that recycles the life-span.The content of Li in the negative electrode active material 62 is preferably 1at%～70at%.Its reason be because, if the content of Li less than 1at%, then energy density diminishes, if the content of Li surpasses 70at%, then is easy to generate arborescence as stated.And, because in this execution mode, be with bigger energy density (that is, being more than the 300F/g) as the static capacity C of the given per unit weight of target as prerequisite, so the content of the Li in the negative electrode active material 62 10at%～70at% more preferably.
[the 4th invention]
Below, in reference to Figure 13, to of the present invention the 4th the invention an execution mode describe.
(preparation of negative electrode active material)
(pre-treatment of aluminium foil)
1), uses the aqueous solution that contains 5.5 quality % hydrochloric acid, 1.5 quality % phosphoric acid and 0.5 quality % nitric acid, 2.0 quality % aluminium chloride as electrolyte.The aluminium foil of thick 110 μ m that will have given composition (do not comprise Li, details are with reference to below table 11) is in being controlled to be 18 ℃ above-mentioned electrolyte, with 10Hz, current density 120mA/cm 2Triangular wave alternating current etching after 10 seconds～27 minutes, clean with ion exchange water.
2) then, these aluminium foils, are cleaned with ion exchange water after 2 minutes～3 minutes with 60 ℃ of dippings in 5.0 quality % aqueous sulfuric acids.
(synthesizing of negative electrode active material)
Aluminium foil and the lithium plate that carried out pre-treatment in advance that will be connected respectively with side of the positive electrode, negative side, above-mentioned is immersed in the electrolyte, is connected respectively and stands facing each other with negative side, side of the positive electrode.And electrolyte is by electrolyte (LiPF 6) and organic solvent (ethylene carbonate (EC): diethyl carbonate (DEC)=1: 1) constitute, concentration is the mixed solution of 1mol/l.Through under this state, be that 25mV is (with respect to Li/Li with the control of Electric potentials of said aluminium foil +), 50 ℃ of following electrolysis and alloying, obtain the negative electrode active material 82 (with reference to Figure 13) of the test No.1D～8D shown in the below table 11.Utilize this synthetic aluminium alloy that contains lithium that obtains to have many pores.Here the said aluminium alloy that contains lithium is also to comprise because of synthesis condition etc. containing some not general names of the aluminium alloy that contains lithium of alloy portion.In addition, said here pore is the general name in some holes of comprising that also pre-treatment condition because of above-mentioned aluminium foil etc. produces.In addition, the length of the opening of pore footpath and pore is defined as followsly.That is, because the section shape of pore is not necessarily circle, therefore the opening of said pore directly is meant the maximum cross section length of the section of pore here.In addition, because also punctulate degree of depth situation about deforming, therefore the length of said pore is meant the maximum length of pore here.The opening of the pore of the negative electrode active material 82 of test No.1D～8D directly is 0.05 μ m～7 μ m, and the ratio in the opening footpath of the length/pore of pore is 7～103.In addition, the distribution of pore is even haply, utilizes the ratio preferred 30%～80% of the shared area of pore in the surface of the above-mentioned synthetic negative electrode active material 82 that obtains.In the distribution of this pore, reflect the distribution of the pore of the above-mentioned aluminium foil that carried out pre-treatment in advance.Electric weight during in addition, according to above-mentioned compound experiment is calculated the lithium content (with reference to below table 11) in this negative electrode active material 82.
[table 11]
Figure BDA00002153499100301
(formation of negative pole)
Shown in figure 13, with utilizing the above-mentioned synthetic negative electrode active material 82 that obtains to use as negative pole.
(preparation of positive active material)
With active carbon (average grain diameter 2.5 μ m, BET specific area: 800～1300m 2/ g) and graphite (average grain diameter 2.0 μ m) with the given mixed shown in the above-mentioned table 11, prepare (with reference to the test No.1D shown in the above-mentioned table 11～8D) as positive active material 84 (with reference to Figure 13).The definition of the graphite containing ratio in the positive active material 84 is quality/(quality of the quality+graphite of active carbon) * 100 (%) of graphite.
(anodal formation)
Shown in figure 13, in utilizing the above-mentioned positive active material for preparing 84, add acetylene black 45%, PV d F5% again, and process paste-like with the N-N-methyl-2-2-pyrrolidone N-.The material of this paste-like is coated on the collector body 83 that is made up of pure aluminum foil, after the drying, carries out crimping and process positive pole.
(electric energy storage device)
Figure 13 is the sketch map that is used to explain as the capacitor of an execution mode of the electric energy storage device of the 4th invention.
Among Figure 13, symbol 80 expression containers, symbol 85 expressions infiltrated with negative electrode active material synthetic in the distance piece of the identical electrolyte of the electrolyte that uses.Through with this above-mentioned negative pole of distance piece 85 usefulness and above-mentioned anodal clamping, and constitute capacitor.That is, distance piece 85 is by negative electrode active material 82 and positive active material 84 clampings.Adapt with positive active material 84 with the negative electrode active material 82 of the test No.1D～8D shown in the table 11, the capacitor that so constitutes is made as test No.1D～8D, be shown in the below table 12.
[table 12]
Figure BDA00002153499100311
Determine the charging voltage of the capacitor that constitutes as illustrated in fig. 13.Then, these capacitors being carried out cyclic test (depth of discharge 20%), is that the period of 95% the time point at initial stage is made as and recycles the life-span with discharge capacity.Simultaneously, obtain energy density (Wh/kg).Its result is shown in the above-mentioned table 12.
Shown in above-mentioned table 12, the charging voltage of test No.1D～7D is 4.4～4.8V, and No.8D compares higher with test.In addition; Though the energy density (capacity) of test No.1D～6D is 90～200Wh/kg; Satisfy given energy density (more than 90～200Wh/kg), yet the energy density (capacity) of test No.7D, 8D is 84,70, is lower than given energy density respectively as target.Become for the energy density (capacity) of test No.1D～6D and can think greatly because have that to comprise the graphite that can embed anion and cationic active carbon be that the negative pole of positive pole quilt and the aluminium alloy system negative electrode active material that contains lithium with porous matter of positive active material makes up.Like this; In test No.1D～6D; To have the structure that the graphite that comprises active carbon is the negative pole combination of the positive pole of positive active material and the aluminium alloy system negative electrode active material that contains lithium with porous matter owing to adopted, so can satisfy the increase of energy density (capacity) and as given these two aspects of life-span (more than 600) that recycle of target.When charging, produce volumetric expansion because of the lithium content in the negative pole increases, yet, therefore can absorb, alleviate the influence that causes by volumetric expansion owing to adopted the negative pole of the aluminium alloy system negative electrode active material that contains lithium in the 4th invention with porous matter.In addition, in order to guarantee big energy density (big capacity) under the situation that recycle the life-span not reducing, preferred so that graphite containing ratios in the positive active material 84 are that 10%～70% mode contains active carbon.
The content of Li in the negative electrode active material 82 is preferably 5 atoms (at) %～70at%.Its reason be because, if the content of Li less than 5at%, then energy density diminishes, if the content of Li surpasses 70at%, then is easy to generate the volume arborescence of electrode.And more preferably the content of Li is 30at%～65at%.
In addition, negative electrode active material 82 preferably also contains the Si of 0.1at%～24at%.Its reason be because, if the content of Si less than 0.1at%, then negative electrode active material 82 will undercapacity, if the content of Si surpasses 24at%, then negative electrode active material 82 will become fragile.
And, though in this execution mode, be that example is illustrated with the aluminium foil of thick 110 μ m, yet not necessarily be defined in this, also can use the aluminium foil of thick about 5 μ m～200 μ m.In addition, in this execution mode, contain the negative electrode active material that the aluminium alloy of the porous matter of lithium is made as utilization, shown in above-mentioned table 11, explained that with Al and Li be the alloy that Si, Sn, Mg are suitably contained in the center.But above-mentioned negative electrode active material also can contain the following Fe of 0.05at%, Cu, Mn, Zn, Ti etc. as unavoidable impurities.
In addition, the electrolyte as to distance piece 85 infiltrations also can adopt by electrolyte (LiBF 4) and the concentration that constitutes of organic solvent { ethylene carbonate (EC): the mixed solution of methyl ethyl carbonate (EMC)=1: 1 } be the electrolyte of 1.5mol/l.
And, though in this execution mode, the structure that does not have collector body is set with respect to negative electrode active material 82 in addition is illustrated, yet is not limited thereto.For example, also can across conductive paste negative electrode active material 82 be crimped on the collector body made of copper lightly and make negative pole, wait collector body to be set in addition with respect to negative electrode active material 82 through operation like this through folder.
Though above execution mode of the present invention is illustrated, yet the present invention is not limited to above-mentioned execution mode, so long as be recorded in the scope of technical scheme, can carries out variously implementing after changing.The application is based on the application of Japanese patent application (the special 2010-095225 of hope of Japan) of Japanese patent application (the special 2010-095224 of hope of Japan) and application on April 16th, 2010 of Japanese patent application (the special 2010-095223 of hope of Japan), the application on April 16th, 2010 of Japanese patent application (the special 2009-013292 of hope of Japan), the application on April 16th, 2010 of on January 23rd, 2009 application, here with its content as with reference to introducing.

Claims (16)

1. a negative electrode active material is characterized in that, is the negative electrode active material of being done by the paper tinsel system of the aluminium alloy system that contains lithium, wherein:
At least the skin section of said paper tinsel body has three-dimensional mesh-shape skeleton and has many pores,
The surface opening rate of said skin section is 10～80%.
2. a secondary cell is characterized in that, comprising:
Have negative pole, the positive pole of the described negative electrode active material of claim 1 and be disposed at said negative pole and said positive pole between ionic conductivity electrolyte.
3. a capacitor is characterized in that, comprising:
Have negative pole, the positive pole of the described negative electrode active material of claim 1 and be disposed at said negative pole and said positive pole between ionic conductivity electrolyte.
4. a negative-electrode active material for secondary battery is the negative-electrode active material for secondary battery of being made by the aluminium alloy of porous matter, and it contains at least a kind in silicon and the tin.
5. negative-electrode active material for secondary battery according to claim 4 is characterized in that,
The content of said silicon and said tin is respectively 0.05～24 atom %, and the content sum of said silicon and said tin is below the 30 atom %.
6. negative-electrode active material for secondary battery according to claim 5 is characterized in that,
The magnesium that contains 0.02～5 atom %.
7. a secondary cell is characterized in that, comprising:
Have each described negative-electrode active material for secondary battery in the claim 4～6 negative pole, have contain lithium and can inhale storage, emit lithium positive active material positive pole and be disposed at said negative pole and said positive pole between ionic conductivity electrolyte.
8. a capacitor is used negative electrode active material, be to use negative electrode active material by the capacitor that the aluminium alloy of porous matter is made, its contain lithium and be selected from silicon and tin at least a kind.
9. capacitor according to claim 8 is used negative electrode active material, it is characterized in that,
The content of said silicon and said tin is respectively 0.05～24 atom %, and the content sum of said silicon and said tin is below the 30 atom %.
10. capacitor according to claim 9 is used negative electrode active material, it is characterized in that,
The magnesium that contains 0.02～5 atom %.
11. a capacitor is characterized in that, comprising:
Have the described capacitor of claim 9 with negative pole, the positive pole of negative electrode active material and be disposed at said negative pole and said positive pole between ionic conductivity electrolyte.
12. a negative electrode active material is the negative electrode active material of being made by the aluminium alloy that contains lithium of the porous matter with pore, wherein:
The opening of said pore directly is below the 5 μ m, but does not comprise zero,
The ratio in the opening footpath of the length of said pore/said pore is more than 10.
13. negative electrode active material according to claim 12 is characterized in that,
The opening of said pore directly is 0.1～5 μ m,
The ratio in the opening footpath of the length of said pore/said pore is 10～100.
14. a secondary cell is characterized in that, comprising:
Have negative pole, the positive pole of claim 12 or 13 described negative electrode active materials and be disposed at said negative pole and said positive pole between ionic conductivity electrolyte.
15. a capacitor is characterized in that, comprising:
Have negative pole, the positive pole of claim 12 or 13 described negative electrode active materials and be disposed at said negative pole and said positive pole between ionic conductivity electrolyte.
16. an electric energy storage device is characterized in that, comprising:
Have the negative electrode active material of making by the aluminium alloy that contains lithium of porous matter negative pole,
Have positive pole that the graphite that comprises active carbon is positive active material,
And be disposed at the ionic conductivity electrolyte between said negative pole and the said positive pole.
CN2010800655516A 2010-04-16 2010-07-23 Negative Electrode Active Material, And Secondary Battery, Capacitor And Electricity Storage Device Each Using The Negative Electrode Active Material Pending CN102812580A (en)

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