CN104051712B - Electrochemical cell - Google Patents

Electrochemical cell Download PDF

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Publication number
CN104051712B
CN104051712B CN201410094009.3A CN201410094009A CN104051712B CN 104051712 B CN104051712 B CN 104051712B CN 201410094009 A CN201410094009 A CN 201410094009A CN 104051712 B CN104051712 B CN 104051712B
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negative electrode
active material
electrode active
addition
cathode
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CN104051712A (en
Inventor
玉地恒昭
渡边俊二
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Seiko Instruments Inc
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Seiko Instruments Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01G11/30—Electrodes characterised by their material
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention, which provides, to be inhibited volume expansion/diminution when charge and discharge due to the electrochemical cell that cracking, reliability is high, high power capacity and cycle life characteristics are excellent occurs in cathode.The electrochemical cell has positive (30), cathode (40), electrolyte containing supporting electrolyte and nonaqueous solvents is formed with partition board (5), the negative electrode active material used in cathode (40) is following particle, i.e., by can be reversibly inserted into while at least containing Si elements, the substance for being detached from the ion of alkali or alkaline earth metal is constituted, in addition, total amount relative to the Si elements contained in negative electrode active material, it adds 1ppm or more and 20% first addition element M below { at least any one element in B or P } respectively by quality ratio or the second addition element R { is selected from In, Sn, Ti, Al, Ge, C, at least one or more element of Zr } in a side or two sides made of particle.

Description

Electrochemical cell
Technical field
The present invention relates to electrochemical cells, more particularly to non-aqueous electrolyte secondary battery or double layer capacitor, ion The electrochemical cells such as capacitor.
Background technology
The electrochemical cells such as the non-aqueous electrolyte secondary battery as electric energy storage device have in the accommodating container of sealing：By Anode and cathode constitute a pair of of polarizing electrode, the partition board between the positive electrode and negative electrode, and be impregnated in anode, cathode and every Electrolyte in plate, containing supporting electrolyte and nonaqueous solvents.Such electrochemical cell is used for mobile phone, PDA, portable The various small electronic apparatus such as game machine especially use laminated-type, cylinder, rectangular shape with the end, coin (button) type more Electrochemical cell.
In addition, SiOx, Si, C be widely used as bearing in the cathode having as the lithium ion battery of electrochemical cell Pole active material.The negative electrode active material and bear that the cathode used in such electrochemical cell can be inserted into/be detached from by lithium ion Pole active material carry out electron transmission conductive agent and to maintain negative electrode active material and conductive agent contact condition bonding Agent is constituted, and by mixing them, forms negative electrode material.Alternatively, forming the negative electrode active for constituting cathode as film In the case of substance, sometimes also using the collector physics for making negative electrode material with being made of metal foils such as copper foil or stainless steels The structure being in direct contact to property.
Since negative electrode active material as described above is amorphous state, so being inserted into the negative electrode active material of amorphous state Volume expansion is generated whens alkaline-earth metal ions such as alkali metal ion or magnesium representated by lithium ion etc., is sent out when lithium ion inserts off Raw contraction drastically, so amorphous particle is it some times happens that cracking.Since electrolyte is contacted with such cracking, re-form SEI (Solid Electrolyte Interface (solid electrolyte interface)：Substance between electrolyte/electrode), negative electrode active The cracking of substance expands because recharge recycles, and if then continue to be cracked, negative electrode active material is fallen off.Therefore, exist While isolating electronic conductivity access, ionic conductivity significantly reduces, so there is the charge/discharge capacity that electrochemical cell occurs The problem of cycle life characteristics degradation phenomenas such as reduction.
Accordingly, with respect to the negative electrode active material based on silicon (Si), propose by being added with the alkali metal such as sodium, potassium, rubidium, magnesium, The alkaline-earth metal such as calcium and/or iron, nickel, cobalt, manganese, vanadium, titanium, niobium, tungsten, molybdenum, copper, zinc, tin, lead, aluminium, indium, bismuth, gallium, germanium, carbon, The metals such as boron, nitrogen, phosphorus or semimetal or nonmetallic etc. LixMySiOz(wherein, 0≤x, 0≤y ＜ 2,0 ＜ z≤4, M are choosing From more than one elements of metal and nonmetalloid in addition to lithium and silicon) constitute negative electrode active material (referring for example to special Sharp document 1).
In addition, the deterioration for cycle life characteristics is proposed for the purpose of assigning electronic conductivity to negative electrode active material Assign the method for natural flaky graphite or expanded graphite (referring for example to patent document 2).
In addition, it is also proposed that by the molten state to negative electrode active material plating by Al, Ti, Fe, Ni, Cu, Zn, Pd, The metal material particle that any one of Ag, In, Sn are constituted assigns electronic conductivity (referring for example to patent document 3).
Prior art document
Patent document
Patent document 1：No. 3405380 bulletins of Japanese Patent Publication No.
Patent document 2：No. 3188853 bulletins of Japanese Patent Publication No.
Patent document 3：Japanese Unexamined Patent Publication 11-250869 bulletins.
Invention content
Problems to be solved by the invention
But the negative electrode active material containing Si elements due to charge and discharge when the Li amounts of storing it is more, so charge and discharge institute companion Some volume changes also increase.Therefore, because the stress that volume change when charge and discharge due to generates, electrical collector occurs bad To change, interior resistance rises, in addition, the capacity deterioration caused by micronizing increases, so the problems such as cycle life characteristics reduce is generated, But, the not adequately addressed above problem representative in the prior art in above patent document 1 ~ 3 etc..
The present invention completes in view of the above problems, it is intended that providing volume expansion/diminution when inhibiting because of charge and discharge And the electrochemical cell that cracking, reliability is high, high power capacity and cycle life characteristics are excellent occurs in cathode.
The means to solve the problem
The inventors of the present invention are to solve to find when the above subject is furtherd investigate, about the negative electrode active material used in cathode Matter, by using at least composition containing Si elements and then containing specific addition element, volume when can inhibit because of charge and discharge is swollen It is swollen/to reduce and be cracked in cathode.It can inhibit rising or the capacity deterioration of interior resistance as a result, it is found that cycle life characteristics carry Height, thereby completing the present invention.
That is, invention described in 1 is electrochemical cell, to have anode, cathode, containing supporting electrolyte and non-aqueous Electrochemical cell made of the electrolyte and partition board of agent, which is characterized in that the negative electrode active material used in the cathode is such as Lower particle, that is, by the ion that can reversibly be inserted into, be detached from alkali or alkaline earth metal while at least containing Si elements Substance constitute, also, relative to the total amount of the Si elements contained in negative electrode active material, add 1ppm respectively by quality ratio It is above and micro- made of 20% the first addition element M as follows below or a side or two sides in the second addition element R Grain：
(1) first addition element M：At least any one element in B or P；
(2) second addition element R：At least one or more element selected from In, Sn, Ti, Al, Ge, C, Zr.
According to the above configuration, firstly, since negative electrode active material due to containing the first addition element M with unbodied state Steadily exist, so when repeating the insertion and disengaging of the alkali metal ions such as lithium because of electrochemical cell charge and discharge, can inhibit Because the volume expansion/contraction generated in cathode is cracked due to when.
In addition, due to negative electrode active material due to containing the second addition element R with it is unbodied it is in stable condition exist, institute When repeating the insertion and disengaging of the alkali metal ions such as lithium because of electrochemical cell charge and discharge, to improve in negative electrode active material Electronic conductivity, to which the uniformity of the charge in negative electrode active material can be improved.When preventing alkali metal ion to be inserted into as a result, Offset, prevents the localization of volume expansion and contraction, thus can inhibit cracking.
In addition, the invention described in 2 is electrochemical cell, which is characterized in that in the above-described configuration, the negative electrode active material Matter is following particle, that is, relative to the total amount of the Si elements contained in negative electrode active material, adds 1ppm respectively by quality ratio Above and particle made of a side or two sides in 1% first addition element M or described, the second addition element R below.
According to the above configuration, it significantly more obtains can inhibit the volume in electrochemical cell charge and discharge because generating in cathode The effect being cracked when expansion/contraction.
In addition, the invention described in 3 is electrochemical cell, which is characterized in that in the above-described configuration, the negative electrode active material Matter is to add 10ppm or more and 1% below described the respectively relative to the total amounts of the Si elements contained in the negative electrode active material One addition element M, 0.5% or more and 2%, the second addition element R below are formed.
According to the above configuration, it significantly more obtains can inhibit the volume in electrochemical cell charge and discharge because generating in cathode The effect being cracked when expansion/contraction.
In addition, the invention described in 4 is electrochemical cell, which is characterized in that in the above-described configuration, the negative electrode active material Matter by Si elements oxide：SiOx(0 ＜ x ＜ 2) is constituted.
According to the above configuration, negative electrode active material is made of the oxide containing Si elements, thus can reduce negative electrode active The inhomogeneities of element when substance synthesizes.Inserting for the alkali metal ions such as lithium is being repeated because of electrochemical cell charge and discharge as a result, When entering with being detached from, the electronic conductivity in negative electrode active material is improved, to which the equal of the charge in negative electrode active material can be improved Even property.It is therefore prevented that offset when alkali metal ion is inserted into, prevents the localization of volume expansion and contraction, thus can inhibit tortoise Split generation.
In addition, the invention described in 5 is electrochemical cell, which is characterized in that in the above-described configuration, the second addition member The Blend proportion of In and Sn are set as 1 by plain R by quality ratio:9.
According to the above configuration, more stably exist with unbodied state due to negative electrode active material, so because of electrification When learning battery charging and discharging and repeating the insertions and disengaging of alkali metal ions such as lithium, the electronics conduction in negative electrode active material is improved Property, to which the uniformity of the charge in negative electrode active material can be improved.Offset when preventing alkali metal ion to be inserted into as a result, is prevented The only localization of volume expansion and contraction, thus can inhibit cracking.
In addition, the invention described in 6 is electrochemical cell, which is characterized in that in the above-described configuration, the negative electrode active material The average grain diameter of matter is 1nm or more and 50 μm or less.
According to the above configuration, significantly more obtain can inhibit in battery charging and discharging because generated in cathode volume expansion/ The effect being cracked when contraction.
Herein, " average grain diameter " illustrated in the present invention refers to be equivalent to has variously-shaped foreign matter grain in addition to spherical The accumulation grain size D of son50Value.
In addition, the invention described in 7 is electrochemical cell, which is characterized in that in the above-described configuration, remove the negative electrode active Other than substance, the cathode also contains to assign the carbon material of electron conduction, also, the carbon material contain carbon tubulation material or At least any one in carbon film-making material.
According to the above configuration, when repeating the insertion and disengaging of the alkali metal ions such as lithium because of electrochemical cell charge and discharge, Electronic conductivity is assigned for the entire outer surface of negative electrode active material particle, improves the electronics conduction of negative electrode active material particle Property, so the offset when alkali metal ion of the thickness direction and horizontal direction in negative electrode layer being prevented to be inserted into, prevents volume Expansion and the localization shunk, thus can inhibit cracking.
The effect of invention
Electrochemical cell according to the present invention, as described above, using the negative electrode active material that is used in cathode to be following micro- Grain composition, that is, by can reversibly be inserted into, be detached from while at least containing Si elements alkali or alkaline earth metal from The substance of son is constituted, in addition, the total amount relative to the Si elements contained in negative electrode active material, is added respectively by quality ratio 1ppm or more and 20% first addition element M below { at least any one element in B or P } or the second addition element R { choosings From at least one or more element of In, Sn, Ti, Al, Ge, C } in a side or two sides made of particle.
It can inhibit volume expansion/diminution when charge and discharge as a result, due to be cracked in cathode, can inhibit the upper of interior resistance Liter or capacity deterioration.
Therefore, it is possible to provide the electrochemical cell that reliability is high, high power capacity and cycle life characteristics are excellent.
Description of the drawings
Fig. 1 is the non-aqueous electrolyte secondary battery for the embodiment for schematically illustrating the electrochemical cell as the present invention And double layer capacitor, or will be used for anode suitable for the electrode of double layer capacitor, non-water power will be suitable for the invention Figure of the electrode of solution electrolitc secondary cell for the mixed capacitor of cathode, (a) is to show that the incorporating section in external packing body is accommodated with Exploded perspective view, (b) of the state of electrode body are sectional view, the oblique view that (c) is the laminar structure for showing electrode body；
Fig. 2 is the non-aqueous electrolyte secondary battery and electric double layer for the embodiment for being shown as the electrochemical cell of the present invention Capacitor, or by suitable for the electrode of double layer capacitor for anode, will to be suitable for the invention nonaqueous electrolyte secondary Process chart of the electrode of battery for the preparation method of the mixed capacitor of cathode；
Description of symbols
1 non-aqueous electrolyte secondary battery (double layer capacitor：Electrochemical cell)
2 external packing bodies
21 container portions
The incorporating sections 21a
22 caps
The incorporating sections 22a
10 electrode bodies
3 positive polar bodies
30 anodes
31 positive electrode collectors
4 negative electrodes
40 cathode
41 negative electrode collectors
5 partition boards.
Specific implementation mode
Hereinafter, the embodiment of the electrochemical cell as the present invention, enumerates non-aqueous electrolyte secondary battery (electric double layer electricity Container) embodiment respectively forming for they is described in detail while with reference to attached drawing.It should be noted that this The electrochemical cell illustrated in invention specifically refers to：The active material and electrolyte that will act as positive or negative pole are accommodated in container Non-aqueous electrolyte secondary battery or double layer capacitor made of interior, or will be used for just suitable for the electrode of double layer capacitor Pole, the mixed capacitor etc. that the electrode for being suitable for the invention non-aqueous electrolyte secondary battery is used for cathode, in this embodiment party It is also illustrated for them in formula.
[non-aqueous electrolyte secondary battery (double layer capacitor)]
The non-aqueous electrolyte secondary battery 1 of the present embodiment as shown in Fig. 1 (a) ~ (c) is so-called laminated-type.Fig. 1 (a) it is to show that the inside in external packing body 2 is accommodated with the exploded perspective view of the state of electrode body 10, is (b) nonaqueous electrolyte two The sectional view of primary cell 1, (c) be show electrode body 10 laminar structure oblique view.It should be noted that for convenience of description, Fig. 1 (a) exploded perspective view is the decomposition being decomposed into the external packing body 2 being integrally formed shown in the 1st container portion 21 and the 2nd container portion Oblique view.
The non-aqueous electrolyte secondary battery 1 is in the concave setting in the inside for the external packing body 2 being made of laminated film Incorporating section 21a, 22a are accommodated with made of electrode body 10 approximate flat nonaqueous electrolyte secondary cell.In addition, being accommodated with electricity The electrolyte of illustration omitted is filled in incorporating section 21a, 22a of the external packing body 2 of polar body 10.
In addition, for the non-aqueous electrolyte secondary battery 1 of present embodiment, the negative electrode active material used in cathode 40 is The composition of following particle, that is, by alkali metal or alkaline earth gold can be reversibly inserted into, be detached from while at least containing Si elements The substance of the ion of category is constituted, in addition, the total amount relative to the Si elements contained in negative electrode active material, distinguishes by quality ratio Add 1ppm or more and 20% the first addition element M as follows below or a side or two sides in the second addition element R and At particle：
(1) first addition element M：At least any one element in B or P；
(2) second addition element R：At least one or more element selected from In, Sn, Ti, Al, Ge, C, Zr.
The external packing body 2 used in the non-aqueous electrolyte secondary battery 1 of present embodiment is for example by nylon film or by aluminium The aluminium laminated film that foil, polypropylene film etc. are sequentially laminated and are bonded is constituted.At this point, the bonding agent of illustration omitted also can be between Between above layers.In the example as shown in Fig. 1 (a), (b), external packing body 2 is by planar observation (plane Visual) is approximate Centre portion be formed with the 1st container portion 21 of concavity incorporating section 21a and be overlapped in the 1st container portion 21 and by inner sealing, be formed with The 2nd container portion 22 of concavity incorporating section 22a is constituted.In addition, in illustrated example, 22 one of the 1st container portion 21 and the 2nd container portion It is formed.
As described above, being obtained as in the inner space for the external packing body 2 being made of aluminium laminated film storage electrode body 10 The method of battery structure, such as following method can be used, that is, load electrode body in the bag-shaped inner space by aluminium laminated film 10, electrolyte is at the same time injected, thermal welding aluminium laminated film carries out closed method after inside defoams.
Alternatively, also can be in advance using the method for preparing the 1st and the 2nd container portion 21,22 respectively, by above-mentioned aluminium laminated film After being placed on mold, apply pressure carry out extrusion process molding, incorporating section 21a, 22a is consequently formed, then incorporating section 21a, 22a loads electrode body 10, at the same time injects electrolyte, is then mutually bonded the edge part in the 1st and the 2nd container portion 21,22. In the case, from the viewpoint of the electrolyte leakage that can prevent from being accommodated in incorporating section 21a, 22a, preferably by these edges Portion is welded to each other or is bonded.
As shown in Fig. 1 (c), electrode body 10 has：It is laminated with by anode 30 and the film-form that constitutes of positive electrode collector 31 just Polar body 3, the film-form negative electrode 4 being made of cathode 40 and negative electrode collector 41 and it is set to these positive polar bodies 3 and negative electrode 4 Between film-form partition board 5 laminar structure.That is, anode 30 is made in electrode body 10 passes through 5 relative superposition of partition board with cathode 40 Composition.In addition, in the example as shown in Fig. 1 (a) ~ (c), electrode body 10 is formed in the same direction and is wound with by these The layered product that each layer of film-form is constituted it is spiral-shaped.
Then, the incorporating section in the 1st and the 2nd container portion 21,22 that is filled in is impregnated in positive polar body 3, negative electrode 4 and partition board 5 The electrolyte of illustration omitted in 21a, 22a.
In addition, positive terminal 31a and negative terminal 41a as external terminal respectively with positive electrode collector 31 and cathode current collection Body 41 respectively connects so that is exported by each collector, constituting for electric current can be generated by these each terminals by being made.Even if non-aqueous solution electrolysis Electrolitc secondary cell 1 is positive terminal 31a and negative terminal 41a states protruding to the outside, also can by by the 1st container portion 21 with The overlapping of 2nd container portion 22 is closed, it is ensured that seal.
Each element for constituting non-aqueous electrolyte secondary battery 1 is described in detail below.
" electrode body "
As described above, the electrode body 10 of present embodiment such as Fig. 1 (a) ~ (c) is shown, have with stipulated number winding successively It is laminated with structure made of the layered product of the positive polar body 3 that film-form is respectively prepared, negative electrode 4 and partition board 5.The lamination of electrode body 10 The winding times of number, i.e. laminar structure be contemplated that battery behavior etc. and suitable for setting.
Electrode body 10 by by the layered product of above-mentioned laminar structure winding be made it is spiral-shaped after, further pressurization so that It forms flat pattern as example as shown and obtains.Then, electrode body 10 is loaded on to the bag being made of aluminium laminated film Inner space so that the positive terminal 31a taken out by electrode body 10 and negative terminal 41a are exported to outside, and then injected The electrolyte of specified amount, after defoaming, thermal welding aluminium laminated film is closed.
(anode)
As anode 30, currently known positive active material, conductive auxiliary agent, adhesive etc. can be used.
First, as a positive electrode active material, it such as can enumerate by molybdenum oxide, mangaic acid lithium compound, ferric phosphate lithiumation Close the lamellar compound etc. that object, cobalt acid lithium compound, lithium nickelate compound, Co-Ni-Mn are constituted, preferably mangaic acid lithium compound, phosphorus Sour iron lithium compound.Due to positive 30 positive active materials containing above example, the heat resistance of non-aqueous electrolyte secondary battery 1 It improves, such as can inhibit the displacement volume caused by the heating in 1 use of reflow treatment or non-aqueous electrolyte secondary battery and (put Electricity Capacity) reduction.
As mangaic acid lithium compound, spinel lithium manganese oxide etc. can be enumerated, Li can be enumerated4Mn5-wM1 wO12 (0 ≤ w ＜ 1, M1Be at least one kind of in Ni, Co, Ti, Fe, Cr, Al, Mo, V, Cu, Nb, Zn, Ca, Mg), (Li2O)z·LiMn2- yM2 yO4(0≤y ＜ 1,0≤z ＜ 1, M2With M1It is identical) etc., wherein the Li of preferred w=04Mn5O12。
As LiFePO4 compound, LiFe can be enumerated1-pM4 pPO4(0≤p≤1, M4For Mn, Ni, Co, Ti, Al, It is at least one kind of in Cr, V, Nb), Li3Fe2-qM5 q(PO4)3(0≤q≤1, M5With M4It is identical) etc., wherein preferred LiFePO4。
As cobalt acid lithium compound, LiCo can be enumerated1-rM6 rO2(0≤r ＜ 1, M6For Mn, Ti, Fe, Cr, Al, Mo, V, It is at least one kind of in Cu, Nb, Zn, Ca, Mg) etc., wherein preferred LiCoO2。
As lithium nickelate compound, LiNi can be enumerated1-sM7 sO2(0≤s ＜ 1, M7For Mn, Co, Ti, Fe, Cr, Al, It is at least one kind of in Mo, V, Cu, Nb, Zn, Ca, Mg) etc., wherein preferred LiNiO2。
In addition, a kind among the above can for example be used alone or two or more is applied in combination by positive active material.
Herein, using particulate positive electrode active material, with regard to its average grain diameter (D50) for, such as in molybdenum oxygen In the case of compound, preferably 0.1 ~ 100 μm, more preferable 1 ~ 10 μm.
In addition, in the case of lithium manganese oxide, preferably 0.1 ~ 100 μm, more preferable 10 ~ 50 μm.
In addition, in the case of lithium iron phosphate cpd, preferably 0.001 ~ 1 μm, more preferable 0.01 ~ 0.1 μm.
If grain size (the D of positive active material50) be less than the lower limiting value of above-mentioned preferred scope, then it is reactive in reflow treatment It improves, so being difficult to operate, if being more than upper limit value, discharge rate has the anxiety of reduction.
It should be noted that " grain size (the D of positive active material in the present invention50) " it is the grain measured using laser diffractometry Diameter refers to median particle diameter.
For the content of the positive active material in anode 30, the work required by non-aqueous electrolyte secondary battery 1 is considered Capacity etc. and determine, preferably 50 ~ 95 mass %, more preferable 70 ~ 88 mass %.If the content of positive active material is above-mentioned preferred More than the lower limiting value of range, be then easy to get to enough displacement volumes, if preferred upper limit value hereinafter, then easily by anode 30 at Type.
Containing conductive auxiliary agent, (by the conductive auxiliary agent used in anode 30, referred to as " positive conductive helps anode 30 sometimes below Agent ").
As positive conductive auxiliary agent, such as furnace black, Ketjen black (Ketjen black), acetylene black, graphite can be enumerated etc. Carbonaceous material.
1 kind among the above can be used alone or two or more is applied in combination by positive conductive auxiliary agent.
In addition, content preferably 4 ~ 40 the mass %, more preferable 10 ~ 25 mass % of the positive conductive auxiliary agent in anode 30.If just The content of pole active material is the lower limiting value of above-mentioned preferred range or more, then is easy to get to enough electric conductivity.In addition, will be electric Pole is shaped to easily molded in the case of piece (pellet) shape.On the other hand, if the content of the positive conductive auxiliary agent in anode 30 is The upper limit value of above-mentioned preferred range is hereinafter, then anode 30 is easy to get to enough displacement volumes.
Anode 30 contains adhesive (adhesive used in anode 30 is known as " positive electrode binder " sometimes below).
As positive electrode binder, currently known substance can be used, such as polytetrafluoroethylene (PTFE) (PTFE) can be enumerated, gathered partially Vinyl fluoride (PVDF), styrene butadiene ribber (SBR), polyacrylic acid (PA), carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA) etc., wherein more preferable Kynoar (PVDF) or its compound (copolymer) (PVDF-HFP).Especially by breast The Kynoar (PVDF) or compound (PVDF-HFP) that liquid polymerize and synthesizes are viscous since water can be used to be used as without using NMP The solvent of mixture, so from the viewpoint of reducing environmental pressure or reducing operating cost more preferably.
In addition, positive electrode binder can be by a kind is used alone or two or more is applied in combination.
The content of positive electrode binder in anode 30 can for example be set as 1 ~ 20 mass %.
The size of anode 30, that is, winding is laminated with the film of the laminar structure of positive polar body 3, negative electrode 4 and partition board 5, is formed Size after spiral-shaped electrode body 10 is determined according to the size of non-aqueous electrolyte secondary battery 1.
In addition, the thickness of anode 30 is also same as described above, determined according to the size of non-aqueous electrolyte secondary battery 1, if not Water-Electrolyte secondary cell 1 is small electronic apparatus laminated-type non-aqueous electrolyte secondary battery, then is for example made 10 ~ 500 μm The film-form of left and right is then for example made 300 ~ 1000 μm or so if Coin shape non-aqueous electrolyte secondary battery.
Anode 30 can be prepared by currently known preparation method.
For example, the preparation method as anode 30, can enumerate and help positive active material and positive conductive optionally Agent and/or positive electrode binder are mixed and made into cathode mix, which is shaped to the side of the arbitrary shapes such as film-form Method.For example, can slurry be mixed with for arbitrary solvent and cathode mix, it is coated on positive electrode collector 31, after the drying, into Row compression forming, is consequently formed.
In addition, as positive electrode collector 31, it is not particularly limited, currently known positive electrode collector can be used.For example, can arrange Enumerate the aluminium foil being made of aluminium alloy or fine aluminium.In addition, the processing of increasing specific surface area is preferably implemented in aluminium foil, sandblasting is preferably implemented Deng exemplified mechanical processing or the processing for carrying out using the chemical method using chemicals such as acid or alkali in advance.
(cathode)
Currently known conductive auxiliary agent, bonding also can be used in addition to the negative electrode active material of the present invention as cathode 40 Agent etc..
First, negative electrode active material of the invention is following particle, that is, by can while at least containing Si elements The substance for the ion for being inserted into, being detached from alkali or alkaline earth metal to inverse property is constituted, in addition, relative to containing in negative electrode active material Si elements total amount, add 1ppm or more respectively by quality ratio and 20% the first addition element M as follows below or Particle made of a side or two sides in second addition element R；First addition element M is by least any one element structure in B or P At；In addition, the second addition element R is made of at least one or more element selected from In, Sn, Ti, Al, Ge, C, Zr.
Herein, the ion of the alkali or alkaline earth metal illustrated in the present invention is to contain supporting electrolyte and non-aqueous The electrolyte of solvent, i.e. be dissolved with supporting electrolyte Non-aqueous Organic Solvents in it is high with the ability of supporting electrolyte solvation Ion, the ion that preferred ion radius is smaller, particularly the mobility of ion at room temperature is high.Further, since it is preferred that in industry To the safe element of human body in production, so in view of such circumstances, preferred Li ions or Na in the ion of alkali metal Ion, the preferred Mg ions in the ion of alkaline-earth metal.
In addition, the negative electrode active material used in cathode 40 is made of following compound：It is as containing above-mentioned ion The substance that the ion of element reversibly can be inserted into and be detached from, and the compound at least containing Si elements.
Herein, the general formula of the negative electrode active material containing Si (silicon) is with composition formula { AxSiOyMzIndicate, in the formula, Elements A is cationic species, is alkali metal ion or alkaline-earth metal ions species, and x is the content x of the ionic species of elements A, is taken The value of following formula { 0≤x≤4.4 }, oxygen amount y are following formula { 0≤y≤2 }.
Be at least any one element in B or P in addition, element M in above-mentioned formula is as the first addition element M, containing In the case of first addition element M, relative to the total amount of the Si elements contained in negative electrode active material, contain by quality ratio 20% or less 1ppm or more and.
In addition, in the present invention, as the second addition element R, can add selected from In, Sn, Ti, Al, Ge, C, Zr at least Wantonly a kind or more element.Containing second addition element R, with identical, phase the case where above-mentioned first addition element M For the total amount of the Si elements contained in negative electrode active material, also contain 1ppm or more and 20% or less by quality ratio.It is such Second addition element R can be used as metallic element and make an addition in negative electrode active material, for example, can also they oxide or The state of nitride is added.
In addition, constituting the Si elements of negative electrode active material and In, Sn, Ti, Al, Ge, C as the second addition element R The part that can be at least its surface is the particle of the state of carbonization.
In addition, with composition formula { AxSiOyMzIndicate negative electrode active material be not complete compound, such as can be make For the compound (matrix) of particle aggregate.In addition, with composition formula { AxSiOyMzThe negative electrode active material that indicates can be by work For the SiO of precursoryMzMiddle electrochemistry is chemically inserted into as the element A of cationic species and obtains, and particularly preferably uses Electrochemical method is inserted into cationic species：Element A.
In the non-aqueous electrolyte secondary battery 1 of present embodiment, by first to the negative electrode active material for constituting cathode 40 The first addition element M is added in matter so that negative electrode active material steadily exists with amorphous state.As a result, because of electrochemistry Battery charging and discharging and when repeating the insertion and disengaging of alkali metal ions such as lithium, can inhibit volume expansion/receipts because being generated in cathode It is cracked when contracting.
In addition, due to by adding the second addition element R into negative electrode active material so that negative electrode active material is with without fixed Shape state steadily exists, so when repeating the insertion and disengaging of the alkali metal ions such as lithium because of electrochemical cell charge and discharge, The electronic conductivity in negative electrode active material is improved, the uniformity of the charge in negative electrode active material improves.Prevent alkali golden as a result, Belong to offset when ion is inserted into, prevents the localization of volume expansion and contraction, thus can inhibit cracking.
Herein, as with above-mentioned composition formula { AxSiOyMzIndicate negative electrode active material precursor SiOyMzWork can be formed For the second particle of the aggregation caused by primary particle, in addition, can be added with the first addition element M or the second addition element R In a side or two sides in the state of form second particle.
The particle size of negative electrode active material is preferably 1nm or more and 50 μm or less in terms of average grain diameter.In addition, cathode is lived Property substance average grain diameter be more preferably 20 μm hereinafter, especially more preferably 1nm ~ 2 μm range.If negative electrode active material Average grain diameter is above range, then significantly obtain can inhibit in battery charging and discharging cathode generate volume expansion/contraction when The effect that cathode 40 is cracked.
In addition, the form as negative electrode active material, is preferably 1nm or more and 50 μm primary below by average grain diameter Average grain diameter made of grain aggregation is that 0.1 μm or more and 100 μm second particle below is constituted.
In addition, the form as negative electrode active material, is more preferably 1nm or more and 2 μm below primary by average grain diameter Average grain diameter made of particle aggregation is that 0.5 μm or more and 4 μm second particle below is constituted.
In addition, in the second particle of above-mentioned negative electrode active material, preferably 85% or more of total volume is for average grain diameter 1nm or more and 8 μm of primary particle below, 90% or more of more preferable total volume be average grain diameter is 1nm or more and 2 μm or less Primary particle.
It should be noted that if the average grain diameter of negative electrode active material is less than 1nm, such as because of reflow treatment or non-aqueous solution electrolysis Reactivity caused by heating in 1 use of electrolitc secondary cell improves, and has the anxiety of damage battery behavior.If in addition, negative electrode active material The average grain diameter of matter is more than 50 μm, then discharge rate has the anxiety of reduction.
For negative electrode active material, i.e. Si elements or the SiO in cathode 40xDeng the content of the compound containing Si elements, Consider displacement volume required by non-aqueous electrolyte secondary battery 1 etc. and determines, preferably 50 mass % or more, more preferable 60 ~ 70 matter Measure %.
It in cathode 40, has the following advantages that, that is, if the content for the negative electrode active material being made of above-mentioned element is above-mentioned It more than the lower limiting value of preferred range, is then easy to get to enough displacement volumes, in addition, if upper limit value hereinafter, then easily by cathode 40 moldings.
In addition, the total amount relative to the Si elements contained in negative electrode active material, added in negative electrode active material first The amount of addition element M or the second addition element R are more preferably 1% or less 1ppm or more and respectively by quality ratio.By further The amount of each addition element added in negative electrode active material is limited to above range, significantly more obtains can inhibit in electrochemistry The effect being cracked by the volume expansion/contraction generated in cathode when battery charging and discharging.
In addition, in the present invention, the oxide for constituting the negative electrode active material of cathode 40 by Si elements can be used：SiOx The composition for the oxide that (0 ＜ x ＜ 2) is constituted and the second addition element R is In and/or Sn.
In this way, since negative electrode active material is made of the oxide containing Si elements, negative electrode active material synthesis can be reduced When element inhomogeneities.As a result, in the insertion and disengaging for repeating the alkali metal ions such as lithium because of electrochemical cell charge and discharge When, the electronic conductivity in negative electrode active material is improved, to which the uniformity of the charge in negative electrode active material can be improved.Cause This, offset when alkali metal ion being prevented to be inserted into prevents the localization of volume expansion and contraction, thus can inhibit and is sent out in cathode 40 Raw cracking.
In addition, in the present invention, the second addition element R added in negative electrode active material can be used by quality ratio by In It is set as 1 with the Blend proportion of Sn:9 composition.
By the way that the second addition element R is set as above-mentioned Blend proportion so that negative electrode active material is more stable with amorphous state Ground exists.As a result, when repeating the insertion and disengaging of the alkali metal ions such as lithium because of electrochemical cell charge and discharge, improves cathode and live Property substance in electronic conductivity, the uniformity of the charge in negative electrode active material improves.It is therefore prevented that alkali metal ion is inserted into When offset, prevent the localization of volume expansion and contraction, thus can inhibit and be cracked in cathode 40.
In addition, in the present invention, cathode 40 can be used and also contain to assign electronics in addition to above-mentioned negative electrode active material The carbon material of electric conductivity, and the carbon material contains the structure of at least any one in carbon tubulation material or carbon film-making material (graphene) At.
In this way, due to cathode 40 contain above-mentioned carbon material, repeated because of electrochemical cell charge and discharge the alkali metal such as lithium from It is that the entire outer surface of negative electrode active material particle assigns electronic conductivity, negative electrode active material plasmid when the insertion and disengaging of son The electronic conductivity of son improves.Prevent thickness direction and the alkali metal ion of horizontal direction in the electrode layer of cathode 40 from inserting as a result, Fashionable offset, prevents the localization of volume expansion and contraction, thus can inhibit and is cracked in cathode 40.
Containing conductive auxiliary agent, (by the conductive auxiliary agent used in cathode 40, referred to as " negative conductive helps cathode 40 sometimes below Agent ").Negative conductive auxiliary agent is identical as positive conductive auxiliary agent.
Cathode 40 contains adhesive (adhesive used in cathode 40 is known as " negative electrode binder " sometimes below).
As negative electrode binder, Kynoar (PVDF), styrene butadiene ribber (SBR), polypropylene can be enumerated Sour (PA), carboxymethyl cellulose (CMC), polyimides (PI), polyamidoimide (PAI) etc., wherein preferred polyacrylic acid (PA) or polyimides (PI), more preferable cross-linking type polyacrylic acid.Additionally, it is preferred that neutralizing the material of polyacrylic acid.
In addition, a kind among the above can be used alone or two or more is applied in combination by negative electrode binder.It should be noted that In the case where polyacrylic acid is used for negative electrode binder, polyacrylic acid is preferably adjusted to pH3 ~ 10 in advance.In this case The adjustment of pH alkaline earth metal hydroxides such as alkali metal hydroxide or magnesium hydroxide such as can be used lithium hydroxide.
It, preferably in advance will be former in the case where polyimides (PI), polyamidoimide (PAI) are used for negative electrode binder Material is dried in 60 DEG C or more of temperature, by raw material dry type mixing.
The content of negative electrode binder in cathode 40 can for example be set as 1 ~ 20 mass %.
Cathode 40 can be prepared by currently known preparation method.
For example, the preparation method as cathode 40, the following methods can be enumerated, that is, by negative electrode active material and optionally Negative conductive auxiliary agent and/or negative electrode binder be mixed and made into negative electrode mix, which is shaped to film-form etc. The method of arbitrary shape.For example, can slurry be mixed with for arbitrary solvent and negative electrode mix, it is coated on negative electrode collector 41 On, after the drying, compression forming is carried out, is consequently formed.But it in the case where PI or PAI is used for adhesive, is done in advance In the mixed processes of dry raw material, it is preferable to use by moisture management be 5%RH or less, more preferably by moisture management be 1%RH with Under hothouse.In addition, as decentralized medium, it can be used and implement dehydration to 100ppm NMP below.
In addition, the method as the coating electrode mixture on negative electrode collector 41, it can be by being fitted in method as follows Preferably select.For example, method of spin coating, scraper method (De ク タ ー ブ レ ー De method), reverse roll method, straight can be enumerated as example Meet the side such as roller (direct roll) method, infusion process, extrusion, extrusion molding, curtain method, scraper method, scraper method (Na イ Off method) Method, but it is not limited to these methods.
In addition, though the size that coating thickness, length or width regard electrochemical cell determines, but coating thickness is after the drying Compressive state under particularly preferably 1 ~ 200 μm.
In addition, the pressing method as sheet material, the method that generally use so far can be used, but particularly preferably mold squeezes Platen press or calender extrusion.As squeeze pressure at this time, although being not particularly limited, preferably 0.2 ~ 3t/cm2.In addition, pressure Prolong preferably 0.1 ~ 50m/ points of the extrusion speed of machine extrusion.In addition, preferred room temperature ~ 200 DEG C of extruding temperature at this time.
By process as described above, cathode 40 can be configured on negative electrode collector 41.
By using the cathode 40 of above-mentioned composition, it can inhibit volume expansion/diminution when charge and discharge due to occur in cathode Cracking, can inhibit rising or the capacity deterioration of interior resistance, so can realize that high reliability, high power capacity and cycle life characteristics are excellent Non-aqueous electrolyte secondary battery 1.
It should be noted that the size or thickness of cathode 40 are identical as anode 30, it can be according to non-aqueous electrolyte secondary battery 1 Size determines, if non-aqueous electrolyte secondary battery 1 is small electronic apparatus laminated-type non-aqueous electrolyte secondary battery, such as 10 ~ 500 μm or so of film-form is made, if Coin shape non-aqueous electrolyte secondary battery, then 300 ~ 1000 μm of left sides are for example made It is right.
In addition, as negative electrode collector 41, such as the copper foil being made of copper alloy or fine copper can be used.Particularly preferably use SUS foils, preferred thickness are 10 μm of SUS304, SUS316 below etc..In the case where SUS foils are used for negative electrode collector 41, It is preferred that implementing the pretreatment of raising surface area to surface with sanding machine or roller etc. in advance.At this point, the effect by improving surface area The anchoring effect of fruit and adhesive, can prevent because charge and discharge with electrode active material dilation caused by volume become The disengaging of active material caused by change.
In addition, the pretreatment can be used chemical method or use mechanical means.Using chemical method, such as It can play anchoring effect by implementing chemical etching to SUS foils surface, electrode active material made to be firmly fixed at SUS foil tables Face.Rising or the capacity deterioration of interior resistance are can inhibit as a result, so high reliability, high power capacity and cycle life characteristics can be realized Excellent non-aqueous electrolyte secondary battery 1.
(electrolyte)
Electrolyte (illustration omitted) is the electrolyte that supporting electrolyte is dissolved in nonaqueous solvents.
As supporting electrolyte, it may be used at the public affairs for being used as supporting electrolyte in the electrolyte of non-aqueous electrolyte secondary battery The substance known, such as LiCH can be enumerated3SO3、LiCF3SO3、LiN(CF3SO2)2、LiN(C2F5SO2)2、LiC(CF3SO2)3、LiN (CF3SO3)2、LiN(FSO2)2Equal organic acids lithium salts, LiPF6、LiBF4、LiB(C6H5)4, the inorganic acids lithium salts such as LiCl, LiBr etc. Lithium salts etc..Wherein, preferably as the lithium salts of the compound with lithium ion conductive, more preferably make under independent or admixture Use LiPF6、LiN(CF3SO2)2、LiN(FSO2)2、LiBF4。
1 kind among the above can be used alone or two or more is applied in combination by supporting electrolyte.
As nonaqueous solvents, considers heat resistance or viscosity required by electrolyte etc. and determine, such as formic acid can be enumerated The formic acid esters such as ethyl ester, propyl formate, n-propyl formate, the propionic esters such as methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate The aliphatic monocarboxylic acids esters such as equal butyrates；The linear carbonates such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate；Carbonic acid is sub- The cyclic carbonates such as ethyl ester (EC), propylene carbonate (PC), carbonic acid 1,2- butylenes (BC), vinylene carbonate (VC)；Diformazan The chain sulfones such as sulfone, ethyl-methyl sulfone；The glycol ethers such as tetraethylene glycol dimethyl ether, ethylene glycol diethyl ether；Sulfolane (SL), γ-fourth Lactone (GBL), 1,2- dimethoxy-ethane (DME), 1,2- diethoxyethane (DEE), 1,2- ethoxymethyl) epoxide ethane (EME), tetrahydrofuran (THF), 1,3-dioxolane (DOL) etc..
The content of supporting electrolyte in electrolyte is contemplated that type of supporting electrolyte etc. and determines, such as preferably 0.1 ~ 3.5mol/L, more preferable 0.5 ~ 3mol/L, particularly preferred 1 ~ 2.5mol/L.Supporting electrolyte excessive concentration in electrolyte or mistake It is low, conductivity is caused to reduce, there is the anxiety for causing harmful effect to battery behavior.
(partition board)
Partition board 5 is between anode 30 and cathode 40, using with big ion permeability and with the exhausted of mechanical strength Velum.
As partition board 5, the film for being used for non-aqueous electrolyte secondary battery partition board so far can be applied without any restriction The partition board of shape, as laminated-type electrochemical cell, can enumerate with because electrochemical cell extremely caused heating due to block sky The alkene such as the polyethylene, the polypropylene of shutdown (shutdown) function in cave, polyamide or polyethylene/polypropylene composite membrane etc..Separately Outside, in button type, such as the glass such as alkali glass, pyrex, quartz glass, lead glass can be enumerated, by polyphenylene sulfide Ether (PPS), polyethylene terephthalate (PET), polyamidoimide (PAI), polyamide, gathers polyether-ether-ketone (PEEK) The non-woven fabrics etc. that the resins such as acid imide (PI) are constituted.In addition, the false polymer as PVdF-HFP can be used (pseudopolymer), EO (ethylene oxide), PO (polyethylene glycol oxide) or their copolymer and polyacrylonitrile etc. is solidifying Glue.
The thickness of partition board 5 is identical as positive 30 or cathode 40 etc., considers the size or partition board of non-aqueous electrolyte secondary battery 1 5 material etc. and determine, such as 5 ~ 300 μm can be set as.
It should be noted that in the present embodiment, although to have the non-of the laminated-type structure as shown in Fig. 1 (a) ~ (c) It is illustrated for Water-Electrolyte secondary cell, but the present invention is not limited to this.For example, it is also possible to for coin-type structure or lead to Cross the opening portion of the heat treatment ceramic system lids such as the seam weld for using made of metal sealing part closing ceramic system vessel The non-aqueous electrolyte secondary battery of structure.
As described above, non-aqueous electrolyte secondary battery (double layer capacitor) 1 according to the present embodiment uses The negative electrode active material used in cathode 40 is the composition of following particle, that is, by can while at least containing Si elements The substance for the ion for being inserted into, being detached from alkali or alkaline earth metal to inverse property is constituted, in addition, relative to containing in negative electrode active material Si elements total amount, add 1ppm or more and 20% first addition element M below respectively by quality ratio { in B or P extremely Few any element } or the second addition element R { at least one or more element for being selected from In, Sn, Ti, Al, Ge, C, Zr } in one Particle made of square or two sides.
It can inhibit volume expansion/diminution when charge and discharge as a result, due to be cracked in cathode, to can inhibit interior resistance Rising or capacity deterioration.
Therefore, it is possible to provide the non-aqueous electrolyte secondary battery 1 that reliability is high, high power capacity and cycle life characteristics are excellent.
" preparation method "
Then, for the system of the non-aqueous electrolyte secondary battery (double layer capacitor) of the electrochemical cell as the present invention Preparation Method, suitable for referring to Fig.1,2 illustrate.
The preparation method of the non-aqueous electrolyte secondary battery of preferred embodiment as present embodiment is to prepare such as Fig. 1 (a) method of laminated-type non-aqueous electrolyte secondary battery 1 shown in ~ (c).
First, as shown in Fig. 1 (c), the positive polar body 3 and cathode current collection of anode 30 are formed on 31 surface of positive electrode collector Insertion partition board 5 is wound between 41 surface of body is formed with the negative electrode 4 of cathode 40, prepares electrode body 10.Then, such as Fig. 1 (a) shown in, electrode body 10 is loaded in the external packing body 2 for being pre-formed with concavity incorporating section 21a and 22a.Then, injection electrolysis Liquid, the defoaming rear enclosed external packing body 2 in inside.
Then, according to fig. 2, to the negative electrode active material and cathode 40 of the embodiment of the electrochemical cell as the present invention It illustrates.
First, simple declaration prepares the negative electrode active material A used in cathode 40xSiOyMzThe method of+R.In addition, conduct The material used, using compound containing Si, Si oxide (SiO), the first addition element M, the second addition element R, alkali metal from The elements A of son or alkaline-earth metal ions, below describes their own details.
First, by the crushing of compound containing Si/refinement (Si refinements) as raw material.
Then, the silica of the first addition element M and high-purity are added/are mixed in the compound containing Si refined, Synthesize SiOyMz (SiOyMzSynthesis procedure).
Then, for the SiO of synthesisyMz, stabilizing process is carried out using the second addition element R.It should be noted that for steady Process is determined, due to can hereinafter describe in detail, so omitting the description herein.By the process, SiO is refinedyMz+ R particles.
Then, using the elements A of the alkali metal ions such as Li, Na, K or alkaline-earth metal ions, to SiOyMzIt is inserted into+R particles Alkali metal ion prepares AxSiOyMz+ R (alkali metal ion insertion process).
Additionally, it is preferred that using SiO in advance before being inserted into alkali metal ionyMz+ R particles form the cathode 40 of arbitrary shape.
Then, each process is described in detail.
As negative electrode active material AxSiOyMzThe compound containing Si of one of the material of+R can classify according to its Si purity etc. For the high semiconductor grade of Si purity and its solar battery grade etc. is subject to, specifically, (the K- being as follows that can classify 1)~(K-5)：
(K-1) the use of the purity synthesized by Siemens Method (Siemens method) is 99.99999999% or more Metallic silicon (Si), in the case that the metallic silicon be column or it is block-like be processed into plate (wafer-like), then add B (boron) or P (phosphorus) is used as dopant.At this point, metallic silicon is the mixture of crystalline silicon (microcrystal silicon, polysilicon), amorphous silicon or the two；
(K-2) it uses through fluidized bed process, metallurgy method, zinc reduction, waterglass method, cast oven process, melting deposition method In any means synthesis purity be 99.99% or more metallic silicon, be column in the metallic silicon or block-like process At plate, then adds B (boron) or P (phosphorus) and be used as dopant.At this point, metallic silicon is crystalline silicon (microcrystal silicon, polysilicon), nothing The mixture of setting silicon or both；
(K-3) using the electric arc furnaces using carbon electrode, the silicon that purity is 96% or more obtained by silica is restored, as Impurity, B (boron) or P (phosphorus) amount to 1% crystalline silicon (microcrystal silicon, polysilicon) below or amorphous silicon；
(K-4) it recycles the cutting swarf of the ingot bar or chip etc. that are generated in photovoltaic cell wafers or semiconductor preparation section or cuts Disconnected residue, come from the mud of draining by discharges such as cutting swarf or cutting apparatus etc. obtained by Si powder；
(K-5) antireflective film is removed by used solar cell, by holding surface electrode or the light of backplate Battery crushing is 1mm hereinafter, the state that the thick pulverulent mixture that logical peracid treatment is removed to metal component is further micronized Si powder.
In addition, the compound containing Si obtained by above-mentioned (K-1) ~ (K-5) can be by (B-1) ~ (B- that will be shown below 12) any one of method combines, and carrying out the preparation section of micronized using experience coarse crushing process, (Si is refined to be prepared Process).
In addition, to first pass through titanium particulate or copper particle or metallic fiber prepared by plasma/atomization in advance (containing straight Diameter is nano level fiber) it is core, using fluidized bed process, also can be obtained micro- in the coating silicon in the surface of metal fine powder or metallic fiber Compound containing Si made of powder.
For example, except (B-1) gas atomization, (B-2) water atomization, (B-3) centrifugal force atomization, (B-4) plasma/ Atomization etc. is atomized other than (Atomization) method, and (B-5) can also be used to the rotary electrode method of high-temperature plasma (Rotating Electrode Process：REP methods), (B-6) bruisher, (B-7) ball mill, (B-8) jet mill, (B-9) Any means in grater, (B-10) sand mill, (B-11) kibbler roll, (B-12) planetary stirring machine are applied in combination.
In addition, crush when, above-mentioned (B-6) bruisher, (B-7) ball mill, (B-8) jet mill, (B-9) grater, (B-10) in sand mill, (B-11) kibbler roll, process is crushed in an inert atmosphere, thus can inhibit compound containing Si Oxidation.Especially in (B-8) jet mill, (B-9) grater, inert gas is used preferably in carrier gas.As such Inert gas species, such as nitrogen or argon gas can be used, if but considering to prepare quality, most preferably argon gas.In addition, at (B-7) In ball mill or (B-10) sand mill, in addition to the dry-type pulverizing or crushing that carry out in an inert atmosphere, preferably and use solvent Wet type under be crushed or crushed.At this point, as solvent, water or organic solvent can be used, but from the sight for improving crush efficiency Point sets out, and it is preferable to use organic solvents.As such organic solvent, except aprotics such as protic polar solvents or ether such as alcohol Other than polar solvent, such as the low molecular weight organic solvent of low boiling point can also be used.In addition, as organic solvent, more preferably boil The halogenated organic solvents such as point low freon or defluorinate Leon.
Especially compound hardness containing Si are high, and pollutant is high by mixed possibilities such as the devices that is used in pulverizing process. Therefore, as (B-6) bruisher of grinding device, (B-7) ball mill, (B-8) jet mill, (B-9) grater, (B-10) sand , it is preferable to use inert material on hard, electrochemistry in grinding machine.Specifically, the inside as grinding device is (in also referred to as Lining) or the material of medium that uses in crushing, it is preferable to use aluminium oxide (Al2O3) or zirconium oxide (ZrO2) etc..In such crushing In process, as crushing atmosphere, it is preferable to use inert atmosphere or ring type solvent etc..
In addition, as negative electrode active material AxSiOyMzThe Si oxide of high-purity can be used in a part for the material of+R, As preparation method, any means of (S-1) ~ (S-3) as follows can be used：
(S-1) to the waterglass (NaSiO of high-purity3) in be added acid, separation, cleaning precipitation gel after forged It burns, crushes after dewatering, thus obtained silica (SiO2)；
(S-2) it after purification, is calcined by the silica gel powder as obtained from the hydrolysis of tetraalkoxysilane, de- It is crushed after water, thus obtained silica；
(S-3) by silicon tetrachloride (SiCl4) gas carry out chemical vapor coating (CVD) after, crush, thus Obtained silica.
Then, by detailed SiOyMzSynthetic method be illustrated in (SiO in following (method -1) ~ (method -3)yMzSynthesis Process)：
(method -1) is by the silica of compound containing Si and high-purity respectively under inert gas or decompression 400 ~ 1600 Heated within the temperature range of DEG C, thus with the state of steam mix, Gu make the mixed vapour of generation be precipitated in reaction vessel/ Change, thus can synthesize the particle SiO as precursoryMz；
The silica of compound containing Si and high-purity is sufficiently mixed by (method -2), by mixed raw material powder in indifferent gas It is heated within the temperature range of 400 ~ 1600 DEG C under body or decompression, generates non-stoichiometric silica vapor, make as precursor Particle SiOyMzThus precipitation/solidification can be synthesized；
(method -3) flows out inert gas by the lower section of vertical cylinder, compound containing Si of spraying respectively into the gas flow With the steam of the silica of high-purity, the two haptoreaction, precipitation/solidification is made thus can be closed in the air-flow of the flowing At.In this case, if obtained powder is the micro mist with desirable grain size, go out from the viewpoint that can omit pulverizing process Hair is preferred.
In addition, in (method -1) and (method -2), as the side that will contain Si compounds and mixed with the silica of high-purity Method can be used these stock dispersions in addition to by the method for the direct dry type mixing of each raw material powder in water, alcohol or other solvents Mixed method.
Specifically, can be by the side such as above-mentioned (B-6) bruisher, (B-7) ball mill, (B-8) jet mill, (B-10) sand mill Method proper combination is adjusted.
In addition, as the SiO that will be synthesizedyMzThe method of micronized, can by above-mentioned (B-6) bruisher, (B-7) ball mill, (B-8) the methods of jet mill, (B-10) sand mill proper combination use.
Above-mentioned (method -1) ~ (method -3) is SiOyMzY values be more than 0 the case where.In the case of y=0, also it may be selected not Mix the silica of high-purity.
In addition, relative to Si elements total amount, by quality ratio the first addition element M additive amount be 1ppm or more and In the case of 20% is below, the second addition element R can not be added.Equally, relative to Si elements total amount, by quality ratio The additive amount of two addition element R be 1ppm or more and 20% it is below in the case of, the first addition element R can not be added.
It should be noted that the SiO of synthesisyMzThe specific surface area of particle preferably 0.05 ~ 1500m2/ g, more preferable 0.1 ~ 150m2/ g, particularly preferred 0.1 ~ 100m2/g。
Then, stabilizing process is illustrated.The stabilizing process is in SiOyMzThe process that surface forms conductive cell envelope. Pass through conductive cell envelope as formation, SiOyMzIt also can steadily ensure to disperse with electrode in the case where repeating charge and discharge Conductive auxiliary agent electrical connection.The conductive cell envelope can carry out mechanical disruption under oxygen-free atmosphere using ball mill.In addition, as this Conductive cell envelope, particularly preferred In, Sn, Ti, Al, Ge, C, Zr.
In addition, dry method plating method or rubbing method etc. can be used.As dry method plating method, plasma spraying or in addition to this can be used Resistance heating vapor deposition, electron beam evaporation plating, molecular beam epitaxy, ion plating (ion plating), ion beam depositing, sputtering etc. PVD method.
Herein, as aforementioned stable process, method as follows can be used：
(D-1) by SiOyMz, the method that is mixed with solvent of carbon dust, adhesive；
(D-2) by Titanium or the particle and SiO of copperyMzIt repeats to mix and crush, obtain to mechanochemistry the side of matrix Method；
(D-3) by SiOyMzIt is mixed with the carbon precursor for making high crystalline carbon dust be carbonized by heating, under reducing atmosphere In SiOyMzThe method that surface passes through the coating carbon precursor of heat resolve.
If the method as shown in above-mentioned D-1 is described in detail, it is used as carbon, can be used petroleum coke, pitch coke The hydrocarbon such as charcoal, methane, propane, benzene, acetylene, cellulose, polyacrylonitrile (PAN), pitch fiber etc. are used as the people of its starting material Make carbon.Additionally, it is preferred that by carbon obtained by being thermally decomposed these starting materials in 1200 DEG C ~ 3000 DEG C, in addition, more preferably Pass through carbon obtained by being handled in 2500 DEG C ~ 3000 DEG C of graphitization temperature.In addition, also can be by furnace black, channel carbon black, hot tearing The carbon blacks class such as method carbon black, lampblack is used for starting material.
In addition, as carbon, carbon obtained by graphite crushes will be particularly preferably thermally expanded, furthermore it is preferred that using the six of carbon The propagation direction of angle wire side is tubular or planar carbon material.Specifically, can be by carbon nano-fiber, carbon nanotube, graphite Alkene is independent or mixes a variety of uses.
In addition, by SiOyMzThe hitherto known carbon material of middle addition and in the case of improving electric conductivity, due to Shape of particle is close to spherical shape, so need to improve the ratio added in electrode, but sometimes due to energy density in this case It reduces, it is advantageous to use the long wealthy carbon material bigger than (length/diameter or plane/thickness).Therefore, for SiOyMzImparting is led The carbon material used under electrical purpose is preferably grown wealthy than big carbon material.Can be single layer as such carbon material The MWCNT (multilayer carbon nanotube) that SWCNT (single-layer carbon nano-tube) or multilayer are formed, for example, can by a diameter of 5nm ~ 20nm, Same diameter, the carbon pipe or carbon fiber that length is Asia mm are used in the carbon material that length is 5 ~ 10 μm.But it is even if wealthy using length Than high carbon material, if the mixing ratio of these carbon fibers increases, compression forming can not be improved or roll when forming electrode by having The tendency of compact density.It is therefore preferable that relative to mixture quality by the content of carbon nano-fiber, carbon nanotube, graphene etc. Control is less than 7wt%.
Herein, arc discharge, laser abrasion, CVD method (chemical vapor-phase growing can be used in carbon nano-fiber, carbon nanotube Method) etc. various methods synthesized, such as can be used Showa Denko K. K gas-phase growth of carbon fibre (VGCF) etc..Make For CVD method as described above, in addition to the substrates method such as alcohol CVD method or SG-CVD methods, it is possible to use DIPS methods, CoMoCAT methods, The gas-bearing formations flow methods such as HiPCO methods, super growth CVD method.
In addition, as graphene, CVD method, the preparation method of distillation using SiC single crystal, stripping method (inclusion can be used Reason stripping or chemical stripping or they be used in combination) the methods of obtain.In the case of especially with CVD method, it can exist in advance SiOyMzThe coating organo-metallic compound (such as ferrocene etc.) containing metallic element as catalyst in surface, formation passes through The nanoscopic catalyst particles that heat or photodegradation generate are kind to there is the particle of the catalyst particle in surface adhesion, on one side So that the hydrocarbon stream of high concentration is flowed upward by vertical lower, carries out 350 DEG C less than 1500 DEG C of heating on one side It is carbonized in fluid bed.At this point, especially by keeping hydrocarbon plasmarized, can be generated in a low temperature of 800 DEG C or less, if The temperature, then can be in the SiO as precursoryMzInside inhibits the uneven of silicon and silica, so as to synthesize suitable high current The negative electrode active material of characteristic.In addition, after being coated with carbon, for the transition metal species as catalyst remaining, acid can be passed through Processing is washed to remove.
Additionally, it is preferred that by being chemically modified to above-mentioned carbon material surface, improve affine with electrolyte or adhesive Property.In this case, such as by strong acid treatment surface, carbonyl is assigned, thus improves the wetability with electrolyte solvent.By This, improve assembling electrochemical battery when impregnation from electrolyte to cathode, can be obtained preparation time shorten effect or improve with The effect of the adhesiveness of adhesive, so also it can be expected that keeping occurring the expansion of the negative electrode active material caused by repeating charge and discharge The effect being connect with electronics when shrinking.
Then, the SiO described below to experience stabilizing processyMzMethod (the alkali metal ion of alkali metal ion is inserted into+R It is inserted into process).Below using use lithium as alkali metal elements A in case of illustrate.
Specifically, can be used dissolved with highconcentration alkyllithium high-purity, impregnate in non-polar organic solvent SiOyMzThe method of+R.At this point, can 1mol/L or more be set as the concentration of lithium alkylide, as the lithium alkylide, such as positive fourth can be used Base lithium or 2- butyl lithiums, tert-butyl lithium etc..In addition, the non-polar organic solvent as high-purity, such as can be molten by pentane It is selected during liquid, hexane solution, n-heptane solution, normal octane solution, n -nonane solution, n -nonane solution etc. are a kind at least arbitrary. In addition, although dip time at this time depends on SiOyMzThe grain size of+R, but preferably at least impregnate 2 hours or more, more preferably impregnate 12 hours or more.But in the case where dip time at this time is set as 144 hours or more, due to reaching equilibrium state, institute Even if unchanged if to impregnate longer time dipping effect.
In addition, as to SiOyMzThe method that alkali metal ion is inserted into+R, preferably doubles as above-mentioned pulverizing process, in ball milling It is carried out as pulverizing process in machine.At this point, organic solvent, since surface tension is low, the dispersibility of grinding bodies is high compared with water, institute By being inserted into alkali metal ion, to make the surface of powder be hardened and crisp, thus can be obtained while improving crush efficiency small Powder.
In addition, as negative electrode active material A is obtainedxSiOyMzSiO forwardly can be used in the method for+RyMzIt is used in+R The method that contact reaction method is inserted into alkali metal ion.
Specifically, by keeping making lithium metal particle or metallic lithium foil and SiOyMz+ R physical contact state, can make from The lithium of sub- state diffuses to SiOyMzIn+R.At this time, or mechanism identical with local cell, in this case, to promote Reaction, preferably in SiOyMzThere are electrolyte between+R and lithium metal.In this case, the character of electrolyte can be liquid, but May be solid electrolyte or polymer dielectric.In SiOyMzIn the case of the electronic conductivity shortcoming of+R, due to sometimes Decomposition product is in SiO obtained by being reduced decomposition because of a part for electrolyteyMzThe surfaces+R form the quilt for hindering lithium ion diffusion Film, it is advantageous to be SiO in advanceyMz+ R assigns electronic conductivity.Below to the details of the method for electronic conductivity as imparting It is described.
In addition, the insertion using catalytic alkali metal ion illustrated in the present invention can form following negative electricities Implement after pole piece material.In addition, using the insertion method of such catalytic alkali metal ion because in assembling electrochemical battery It is preceding implementation and can be described as pre-doping.
In addition, as negative electrode active material A is obtainedxSiOyMzSiO forwardly can also be used in the method for+RyMzMake in+R The method for being electrochemically inserted into alkali metal ion.
Such electrochemical method can be prepared after electrochemical cell assembling in electrochemical cell or in electrochemical cell Carried out in electrochemical cell or outside electrochemical cell during process, can example go out the methods of (1) as follows ~ (3)：
(1) by SiOyMzElectrode is as one obtained by the mixture of+R and conductive agent and adhesive etc. is shaped to regulation shape The electrode (working electrode) of side using lithium metal or contains electrode (to electrode) of the substance as the other side of lithium, is led with lithium ion Electrical nonaqueous electrolyte contact, keeps two electrodes opposite, constitutes electrochemical cell, working electrode is in the side for carrying out cathode reaction To with current electrifying appropriate, to the SiO at working electrode tipyMzIt is inserted into lithium ion in+R, thus obtains negative electrode active material AxSiOyMzThe method of+R；
(2) by SiOyMzThe mixture of+R and conductive agent and adhesive etc. is shaped to regulation shape, by lithium or the alloy of lithium Electrode obtained by laminated electrode is made is crimped or contacted as cathode, be inserted into non-aqueous electrolyte secondary battery Deng with it.Then, It is contacted with electrolyte in electrochemical cell by the laminated electrode, forms a kind of local cell, it is by self-discharge that lithium is electric It chemically stores in SiOyMzIn+R, negative electrode active material A is thus obtainedxSiOyMzThe method of+R；
(3) it constitutes SiOyMz+ R be used as negative electrode active material, by containing lithium, can store release lithium ion substance be used as The non-aqueous electrolyte secondary battery of positive active material.It then, will be by by charging before being used as electrochemical cell and using The lithium ion that anode is released is stored in the SiO as cathode precursoryMzIn+R, negative electrode active material A is thus obtainedxSiOyMz+ R's Method.
By the various methods as shown in above-mentioned (1) ~ (3), negative electrode active material A can be obtainedxSiOyMz+R.In addition, making In the case of electrochemically, or the lithium ion that can be reversibly inserted into/be detached from it will be present in anode When being moved to cathode by anode, in the electrochemical cell of composition, negative electrode active material A is electrochemically obtainedxSiOyMzThe side of+R Method.
In this way, by undergoing Si refinements, SiOyMzSynthesis procedure, stabilizing process, alkali metal ion are inserted into process, can Prepare the non-aqueous electrolyte secondary battery 1 of the present invention.
Preparation method according to the present embodiment can make to bear by adding the first addition element M into negative electrode active material Pole active material steadily exists with amorphous state, so can prepare can inhibit because being born in electrochemical cell charge and discharge The non-aqueous electrolyte secondary battery 1 being cracked when volume expansion/contraction that pole 40 generates.
In addition, by adding the second addition element R into negative electrode active material, negative electrode active material can be made with amorphous State steadily exists, so the electronic conductivity in negative electrode active material is improved in electrochemical cell charge and discharge, so as to carry The uniformity of charge in high negative electrode active material can prevent the body of cathode 40 caused by offset when alkali metal ion is inserted into Localization product expansion and shunk can prepare the non-aqueous electrolyte secondary battery 1 that cracking can be inhibited to occur.
By step as described above, the non-aqueous electrolyte secondary battery (double layer capacitor) of present embodiment can be obtained 1。
Preparation method according to the present embodiment can make to bear by adding the first addition element M into negative electrode active material Pole active material steadily exists with amorphous state, so can prepare can inhibit because being born in electrochemical cell charge and discharge The non-aqueous electrolyte secondary battery 1 being cracked when volume expansion/contraction that pole 40 generates.
In addition, by adding the second addition element R into negative electrode active material, negative electrode active material can be made with amorphous State steadily exists, so the electronic conductivity in negative electrode active material is improved in electrochemical cell charge and discharge, so as to carry The uniformity of charge in high negative electrode active material can prevent the body of cathode 40 caused by offset when alkali metal ion is inserted into Localization product expansion and shunk can prepare the non-aqueous electrolyte secondary battery 1 that cracking can be inhibited to occur.
Embodiment
Then, embodiment and comparative example are shown, the present invention is further illustrated.It should be noted that the present invention is not because of this reality It applies example and limits its range, electrochemical cell according to the present invention can become in the range of not changing the main points of the present invention More implement.
[embodiment 1]
In embodiment 1, first, as electrochemical cell, the laminated-type non-aqueous solution electrolysis as shown in Fig. 1 (a) ~ (c) is prepared Electrolitc secondary cell.
In the present embodiment, as shown in Fig. 1 (a), external packing body 2 is to be sequentially laminated nylon layer (25 μm), aluminium foil (40 μ M), the aluminium laminated film of polypropylene layer (30 μm).
In addition, negative electrode 4 has cathode 40 and negative electrode collector 41.Cathode 40 uses the negative electrode active material of following present invention Matter, conductive auxiliary agent and adhesive are constituted, and are formed in the two sides for the negative electrode collector 41 being made of the foil of fine copper.
In addition, positive polar body 3 has anode 30 and positive electrode collector 31.Anode 30 uses positive active material, conductive auxiliary agent It is constituted with adhesive, is formed in the two sides for the positive electrode collector 31 being made of the foil of fine aluminium.
Partition board 5 is configured between negative electrode 4 and positive polar body 3.
For electrode body 10, by the layered product being made of each layer of these film-forms in equidirectional winding.
Use is with 1 in the nonaqueous electrolyte for constituting electrolyte:1:2 volume ratio is mixed with PC:EC:The solvent of EMC The middle LiFP that 1M/L is dissolved with as supporting electrolyte6Electrolyte.
The size of the non-aqueous electrolyte secondary battery of preparation is width 21mm, long 30mm, high 3mm.
Herein, the SiO as the negative electrode active material precursor used in cathode 40y(0≤y ＜ 2), by heater temperature Degree is heated to 1400 DEG C or more, makes silica (SiO2) powder and silicon (Si) powder distinguish powder compression forming and the material for preparing Material gasifies in a vacuum, by the vapour plating on SUS substrates, thus obtains.The group of the substance becomes SiO.
Then, which is directly placed into the tank of agate ball mill, and then by the ball of agate together with ethyl alcohol Input, thus crushes.At this point, at the initial stage of crushing, is operated 72 hours using the ball of a diameter of 8mm, thus carries out coarse crushing, In a fractionated, the ball for further using a diameter of 2mm operates 72 hours, thus carries out Crushing of Ultrafine.
Then, after the SiO particles after crushing are fully dry, be classified as 10 μm hereinafter, with as conductive auxiliary agent After expanded graphite mixing, using ball mill, with SiO surface adhesions while being crushed expanded graphite, thus carry out coating.This When, expanded graphite, to the faces d002 cleavage (cleavage), is also easy to produce carbon film-making material (graphene) by ball mill, high in activity It is contacted with SiO under state, firm coherent condition is made, thus implement carbon coating.
Herein, the preparation condition of negative electrode mix and shown in steps are as follows.
First, as adhesive, lithium hydroxide (LiOH/ (H are used2O)n) aqueous solution to by carboxyl-content be 50 ~ 70% Cross-linking type polyacrylic resin (and the pure medicine polyacrylic acid of light) powder be added purified water in dissolved obtained by it is water-soluble Liquid implements neutralisation treatment, makes PH substantially 7.
Then, conductive auxiliary agent is added in the adhesive of front and is disperseed.At this point, as conductive auxiliary agent, graphite is used (Japanese blacklead thin slice graphite：CMX), and then addition is disperseed by the SiO of coating carbon obtained by the above method.The stone Substantially 5 μm of the grain size of ink.In addition, the Blend proportion of SiO and graphite, carbon fiber are set as active matter shown in following table 1 at this time Matter number 2-1.In addition, making planetary stirring mixer (K102 types) using Kurabo (Network ラ ボ ウ) in dispersion, prepare negative Pole mixture paste.
Then, roller is used after the drying in the two sides for which being spread evenly across to the copper foil that thickness is 20 μm Press compression is molded, and prepares negative electrode sheet material (negative electrode that cathode is laminated on negative electrode collector).The negative electricity pole piece The thickness of material is 70 μm.
In addition, anode 30 is prepared according to step as follows.
First, by as a positive electrode active material complex Li-Mn-oxide, as the graphite of conductive material, as adhesive Kynoar mixing (be by quality ratio 85:5:10) it, is scattered in the n-methyl-2-pyrrolidone as solvent, makes Standby cathode mix slurry.
Then, which is coated on the aluminium foil that thickness is 20 μm, after the drying, is compressed with roll squeezer Molding prepares anode electrode sheet material (positive polar body that anode is laminated on positive electrode collector).
Then, anode electrode sheet material and negative electrode sheet material are cut, after positive terminal, negative terminal are installed respectively, The lithium metal that thickness is 8 μm is pasted on negative electrode sheet material, and the microporous polyethylene film clapboard that thickness is 20 μm is inserted into just Between lithium metal on pole electrode sheet and negative electrode sheet material, stipulated number is wound in length direction, thus prepares battery member Part (electrode body).
In addition, as outer packing, using being sequentially laminated nylon layer (25 μm), aluminium foil (40 μm), polypropylene layer (30 μm) Aluminium laminated film.At this point, the cell device prepared according to above-mentioned steps is loaded on, to be shaped to approximate bag-shaped aluminium layer ironed In film bag, inject by LiBF4(a concentration of 1mol/l) and propylene carbonate, ethylene carbonate, methyl ethyl carbonate mixed solvent (volume ratio 1:1:2) electrolyte constituted, thermal welding aluminium laminated film, is thus closed after defoaming.
Then, by the electrochemical cell of preparation in being placed at room temperature for 1 week, to being used as negative electrode active material in negative electrode sheet material The SiO of matter carries out lithium doping.
Then, by a part of severing of aluminium laminated film, keep the gas of generation when to SiO progress lithium dopings ironed by aluminium layer It is released in film, thermal welding aluminium laminated film, is thus closed again.
Then, for the electrochemical cell prepared according to above-mentioned steps, cycle life characteristics are evaluated under the following conditions.
For cycle life characteristics experiment, at normal temperatures (24 DEG C), with the constant-current charge of 100 μ A to end of charge voltage It keeps constant voltage after reaching 3.3V for 3.3V 96 hours, thus charges.Then, by 15 μ A constant-current discharges to electric discharge Final voltage is that 2.0V is calculated as 1 cycle, carries out to 5 times recycling.At this point, capacity maintenance rate is calculated as the { (work of the 5th cycle The displacement volume of capacity/the 4th cycle) × 100.
The preparation condition of embodiment 1 and the negative electrode active material of following each embodiments 2 ~ 21 and comparative example 1 is illustrated in down In list 1, at the same time it will be illustrated in following table 2 as the Blend proportion of the SiO of precursor and graphite, carbon fiber, in addition, will follow The evaluation result of ring life characteristic is illustrated in following table 3 ~ 7.
[table 1]
[table 2]
[table 3]
Embodiment is numbered Active material is numbered Blend proportion is numbered Displacement volume (body weight (g) before mAh/) Recycle sustainment rate
Embodiment 1 1-2 H-1 1326 91.8
Comparative example 1 1-1 H-1 1056 78.8
[table 4]
Embodiment is numbered Active material is numbered Blend proportion is numbered Displacement volume (body weight (g) before mAh/) Recycle sustainment rate
Embodiment 1 1-2 H-1 1326 91.8
Embodiment 2 1-2 H-2 1613 89.5
Embodiment 3 1-2 H-3 1349 91.0
Embodiment 4 1-2 H-4 1034 87.7
Embodiment 5 1-2 H-5 411 100.3
[table 5]
Embodiment is numbered Active material is numbered Blend proportion is numbered Stabilizing process Displacement volume (body weight (g) before mAh/) Recycle sustainment rate
Embodiment 1 1-2 H-1 Nothing 1326 91.8
Embodiment 6 1-2 H-1 Have 1516 99.9
[table 6]
Embodiment is numbered Active material is numbered Blend proportion is numbered Stabilizing process Displacement volume (body weight (g) before mAh/) Recycle sustainment rate
Embodiment 7 2-1 H-1 Have 1515.6 99.9
Embodiment 8 2-2 H-1 Have 1515.4 99.9
Embodiment 9 2-3 H-1 Have 1500.4 100.8
Embodiment 10 2-4 H-1 Have 1346.0 87.7
Embodiment 11 3-1 H-1 Have 1515.6 99.9
Embodiment 12 3-2 H-1 Have 1515.4 99.9
Embodiment 13 3-3 H-1 Have 1500.4 100.9
Embodiment 14 3-4 H-1 Have 1364.0 87.9
Embodiment 15 4-1 H-1 Have 1364.0 99.9
Embodiment 16 4-2 H-1 Have 1364.0 101.8
[table 7]
Embodiment is numbered Active material is numbered Blend proportion is numbered Stabilizing process Displacement volume (body weight (g) before mAh/) Recycle sustainment rate
Embodiment 17 5-1 H-1 Have 1503.4 89.5
Embodiment 18 5-2 H-1 Have 1364.0 89.5
Embodiment 19 5-3 H-1 Have 1364.0 89.5
Embodiment 20 5-4 H-1 Have 1295.8 89.5
Embodiment 21 5-5 H-1 Have 1091.2 89.5
[embodiment 2 ~ 21]
[comparative example 1]
In embodiment 2 ~ 5 (also including embodiment 1) as shown in table 4, for the system of the electrochemical cell of embodiment 1 Standby condition, as the conductive auxiliary agent used when preparing negative electrode mix, except graphite (Japanese blacklead thin slice graphite, CMX) with Outside, carbon fiber (Showa electrician's gas-phase growth of carbon fibre is added：VGCF).A diameter of 0.15 μm of the carbon fiber, length is substantially It is 10 μm.In addition, change the Blend proportion of SiO and graphite, carbon fiber according to ratio shown in table 2, in addition to this with above-mentioned reality It applies example 1 and prepares non-aqueous electrolyte secondary battery in the same manner, cycle life characteristics are evaluated according to identical method, the results are shown in In table 4.
In addition, in embodiment 6 as shown in table 5 (also including embodiment 1), added into the SiO as precursor C, Ti, by be granulated/the stabilizing process implementation of whole grain handles, in addition to this prepare non-water power identically as above-described embodiment 1 Electrolitc secondary cell is solved, cycle life characteristics are evaluated according to identical method.
In addition, in the embodiment 7 ~ 21 as shown in table 6,7, according to the condition of each active material number as shown in Table 1 Change the preparation condition of negative electrode active material, and then add C, Ti into the SiO as precursor, by be granulated/whole grain Stabilizing process implementation is handled, and in addition to this non-aqueous electrolyte secondary battery is prepared identically as above-described embodiment 1, according to identical Method evaluates cycle life characteristics.
[evaluation result]
Active material number 1-1 ~ 5-5 shown in table 1 is the negative electrode active material precursor of each embodiment and comparative example Preparation condition, Blend proportion number shown in table 2 are the blending condition of precursor in cathode, graphite and carbon fiber.In addition, in table In 3 ~ 7, in addition to the active material of each embodiment and comparative example number and Blend proportion number, it is also shown that displacement volume and cycle are tieed up The guide look of holdup (cycle life characteristics).
As shown in 1 ~ table of table 7, it is known that have and use negative electrode active material specified in the present invention as negative electrode active material Cathode made of embodiment 1 ~ 21 non-aqueous electrolyte secondary battery recycled at 5 times after cycle sustainment rate be 87.7% More than, cycle life characteristics are excellent.Especially for embodiment 7 ~ 9, embodiment 11 ~ 13, embodiment 15 and 16, due to cycle Sustainment rate is about 100%, it is known that cycle life characteristics are more excellent.In addition, though do not recorded in table, but the second addition is first In the case that the mass ratio of plain R is set as 0.5% or 2%, the cycle sustainment rate roughly the same with embodiment 7 ~ 16 is also obtained.
On the other hand, in the present invention as defined in other than range under conditions of prepare the negative electrode active material used in cathode Comparative example 1 in, cycle sustainment rate be 78.8%, with embodiment 1 ~ 21 compared with significantly variation.Think the reason is that due to than It is not added in the first addition element M or the second addition element R specified in the present invention compared with the negative electrode active material prepared in example 1 It is any, so, when the charge and discharge of each cycle volume expansion/diminution of cathode due to be cracked in cathode, occur in it is electric Resistance rises or capacity deterioration.
It should be noted that although be not used as embodiment record, use Al, Ge, Zr as the feelings of the second addition element R Under condition, cycle sustainment rate is still 87.7% or more.It follows that adding the case where Al, Ge, Zr are as the second addition element R Under, it is identical as the case where using In, Sn, Ti, C, the excellent electrochemical cell of cycle life characteristics also can be obtained.
In addition, having the electrochemical cells such as the non-aqueous electrolyte secondary battery of the cathode of present embodiment is suitable for such as electricity Pressure value is the miniature portable instrument of the power supply of 2 ~ 3V.
As indicated above, it is known that due to having the cathode for having used negative electrode active material specified in the present invention, can be had There are the electrochemical cells such as the non-aqueous electrolyte secondary battery of excellent cycle life characteristics.
Industrial availability
Electrochemical cell according to the present invention, due to having above-mentioned cathode, volume expansion/contracting when can inhibit because of charge and discharge It is small and be cracked in cathode, to can inhibit rising or the capacity deterioration of interior resistance.Thus, it is possible to provide reliability height, Gao Rong Amount and the excellent electrochemical cell of cycle life characteristics.Therefore, by applying the present invention to such as in various electronic instruments The electrochemical cells such as the non-aqueous electrolyte secondary battery (double layer capacitor) that field uses, also can be to the property of the various instruments of raising It can contribute.

Claims (5)

1. electrochemical cell is to have anode, cathode, the electrolyte containing supporting electrolyte and nonaqueous solvents and partition board to form Electrochemical cell, which is characterized in that
The negative electrode active material used in the cathode is following particle, that is, by least containing Si elements, following formula AxSiOyMz+ R can reversibly be inserted into, be detached from the ion of alkali or alkaline earth metal substance while expression is constituted, and And relative to the total amount of the Si elements contained in negative electrode active material, 1% or less 1ppm or more and is added respectively by quality ratio As follows the first addition element M or a side or two sides in the second addition element R made of particle：
First addition element M：At least any one element in B or P,
Second addition element R：At least one or more element selected from In, Sn, Ti, Al, Ge, C, Zr,
Also, the cathode contains the graphite and carbon fiber as the carbon material to assign electron conduction, and, as described The SiO of the precursor of negative electrode active materialyMzThe Blend proportion of+R and the graphite, the carbon fiber is following formula SiOyMz+R：Graphite： Carbon fiber=45:45:0、45:40:5、45:35:10 range,
Wherein, the formula AxSiOyMzIn+R, A is cationic species, is the member of alkali metal ion or alkaline-earth metal ions species Element, x are the content x of the ionic species of A, remove the value of formula 0≤x≤4.4, and y is oxygen amount, are that following formula 0≤y≤2, M add for first Added elements, R are the second addition element.
2. the electrochemical cell of claim 1, which is characterized in that the negative electrode active material is relative to the negative electrode active material The total amount of the Si elements contained in matter add respectively 10ppm or more and the 1% first addition element M below, 0.5% or more and The 2% second addition element R below is formed.
3. the electrochemical cell of claims 1 or 2, which is characterized in that the negative electrode active material by Si elements oxide： SiOxIt constitutes, x is 0 ＜ x ＜ 2 of following formula.
4. the electrochemical cell of claims 1 or 2, which is characterized in that the second addition element R is by quality ratio by In and Sn Blend proportion be set as 1:9.
5. the electrochemical cell of claims 1 or 2, which is characterized in that the average grain diameter of the negative electrode active material is 1nm or more And 50 μm or less.
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