CN103872292B - Anode for nonaqueous electrolyte secondary battery active material and its manufacture method - Google Patents
Anode for nonaqueous electrolyte secondary battery active material and its manufacture method Download PDFInfo
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- CN103872292B CN103872292B CN201310677119.8A CN201310677119A CN103872292B CN 103872292 B CN103872292 B CN 103872292B CN 201310677119 A CN201310677119 A CN 201310677119A CN 103872292 B CN103872292 B CN 103872292B
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- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 16
- 239000011149 active material Substances 0.000 title claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 105
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 49
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 46
- 238000000576 coating method Methods 0.000 claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 38
- 238000012545 processing Methods 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- 239000011246 composite particle Substances 0.000 claims abstract description 18
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 15
- 239000007773 negative electrode material Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 13
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- 238000007323 disproportionation reaction Methods 0.000 description 9
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- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- 239000011261 inert gas Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical class [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
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- 239000002002 slurry Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 102100028168 BET1 homolog Human genes 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
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- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/362—Composites
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
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- 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
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention provides anode for nonaqueous electrolyte secondary battery active material and its manufacture method.The high battery capacity for maintaining silica can be obtained by providing, and first efficiency for charge-discharge height, the excellent rechargeable nonaqueous electrolytic battery of cycle characteristics aspect are effectively coated to particle and manufacture method as negative electrode active material and with the lithium rechargeable battery and electrochemical capacitor using its negative pole.The particle of the composite particles for the structure being scattered in selected from silicon oxide particle, with nano silicon particles in Si oxide and their hybrid particles is not passed through after organic gas is heat-treated by the manufacture method for the negative electrode active material being made up of the coated particle with carbon coating, and the heat treated particulate of acquisition is carried out into chemical vapor deposition in organic gas（CVD）Processing；It is characterized in that the temperature by above-mentioned heat treatment（Maximum temperature in heat treatment）T1 is set to, by the temperature in chemical vapor deposition process（Maximum temperature in chemical vapor deposition process）It is set to T2, and T1 ＞ T2.
Description
Technical field
The present invention relates to as lithium ion secondary battery cathode active material in use, with containing high first charge and discharge
Electrical efficiency, good cycle characteristics carbon coating coated particle manufacture method, lithium ion secondary battery cathode active matter
Matter and the lithium rechargeable battery and electrochemical capacitor that the negative electrode active material is used for negative pole.
Background technology
In recent years, along with the notable development of portable electron device, communicator etc., from the small-sized of economy and device
Change, from the viewpoint of lighting, need the rechargeable nonaqueous electrolytic battery of high-energy-density strongly.So far, as this non-aqueous
The high capacity countermeasure of electrolyte secondary battery, it is known that for example in negative material using B, Ti, V, Mn, Co, Fe, Ni, Cr,
Nb, Mo etc. oxide and its method for composite oxides, the M that will quickly be cooled down through liquation100-xSix（X >=50 atom %, M=
Ni、Fe、Co、Mn）The method used as negative pole, use in negative material silicon oxide method, in negative material
It is middle to use Si2N2O、Ge2N2O and Sn2N2O method etc..
Wherein, it is believed that silica although battery capacity is smaller compared with silicon, but if with carbon phase ratio, in terms of unit mass,
It is higher 5-6 times than its, and volumetric expansion is also smaller, is easily used as negative electrode active material.But because silica can not
Inverse capacity is big, initial efficiency is very low for 70% or so, therefore, it is necessary to make positive pole actually in the case where making battery
Battery capacity becomes superfluous, and can not expect the capacity of only quite 5-6 times of units activity material increases the increasing of the battery capacity of part
Add.And, it is also desirable to improve cycle characteristics.
On the other hand, because silica is insulator, electric conductivity can be assigned by some means.As imparting electric conductivity
Method, method that the particle conductive with carbon etc. mix can be enumerated, coated side is carried out to particle surface by carbon coating
Method and by both approaches combine etc..As coated method is carried out by carbon coating, preferably by composite particles in organic matter gas
Chemical vapor deposition is carried out in body（CVD）Method, by heat treatment when into reactor import organic gas can efficiency
Carry out well.
Prior art literature
Patent document
Patent document 1：Unexamined Patent 11-269647 publications
Patent document 2：JP 2004-047404 publications
The content of the invention
The invention solves problem
It is an object of the present invention to obtain while the high battery capacity of silica is maintained, first efficiency for charge-discharge height,
The excellent rechargeable nonaqueous electrolytic battery in terms of cycle characteristics, there is provided as negative electrode active material effectively be coated to particle and its
Manufacture method, and lithium rechargeable battery and electrochemical capacitor with the negative pole using the negative electrode active material.
Means for solving the problems
The present inventor has made intensive studies to achieve these goals, to realize the initial efficiency for improving silica simultaneously
With the aspect of cycle characteristics two and studied.Carbon coating can not only assign electric conductivity, and from because producing gas
Caused electrode expansion and the reactive aspect of electrolyte exerted one's influence to cycle characteristics are set out, it is desirable to subtract specific surface area
It is small and reduce contact area.But from the relation of the thickness with film, it is impossible at will increase particle diameter, by the table of carbon coating
It is effective that face, which smooths out,.In addition, for silica, there is the property reduced by being heat-treated specific surface area, opened from about 900 DEG C
Beginning slowly reduces.Although being also shown since about 1200 DEG C due to the change of size distribution caused by sintering, this be due to
The change of fine pore present on surface.Conversely, because the thermal histories after vapour deposition, carbon coating have specific surface area increase
Tendency, in order to improve initial charge/discharge efficiency and cycle characteristics two simultaneously in terms of, it is necessary to not increase specific surface area and carry out
Disproportionation.
The result of research finds silica carrying out chemical vapor deposition（CVD）Process in, be not passed through organic matter gas
Body and heat treatment is carried out to amorphous silicon oxide particle in advance and is allowed to disproportionation, afterwards with the temperature lower than disproportionation temperature by
Chemical vapor deposition is carried out in organic gas（CVD）BET specific surface area, can be suppressed to low value by processing, if by acquisition
Coated particle is used as anode for nonaqueous electrolyte secondary battery active material, then can obtain efficiency for charge-discharge in the early stage and circulation is special
Property the excellent rechargeable nonaqueous electrolytic battery of aspect, so as to complete the present invention.
Therefore, the invention provides following inventions.
[1] system for the anode for nonaqueous electrolyte secondary battery active material that is made up of the coated particle with carbon coating
Make method, its by selected from silicon oxide particle, have nano silicon particles be scattered in structure in Si oxide composite particles and it
Hybrid particles particle after not being passed through and being heat-treated under organic gas, to the heat treated particulate that is obtained organic
Chemical vapor deposition is carried out in thing gas（CVD）Processing, it is characterised in that by the temperature of above-mentioned heat treatment（In heat treatment most
High-temperature）T1 is set to, by the temperature in chemical vapor deposition（Maximum temperature in chemical vapor deposition process）It is set to T2, and T1
＞ T2.
[2] manufacture methods of the as described in [1], wherein T1 are 900-1300 DEG C.
[3] manufacture methods of the as described in [1] or [2], wherein the coated particle is to disperse with nano silicon particles
There is the coated particle of carbon coating on the surface of the composite particles of structure in Si oxide.
[4] the anode for nonaqueous electrolyte secondary battery active material that is made up of the coated particle with carbon coating, it is logical
Following method is crossed to obtain：By compound of the structure being scattered in selected from silicon oxide particle, with nano silicon particles in Si oxide
The particle of grain and their hybrid particles is not after being passed through and being heat-treated under organic gas, to after the heat treatment that is obtained
Particle carries out chemical vapor deposition in organic gas（CVD）During processing, by the temperature of above-mentioned heat treatment（In heat treatment
Maximum temperature）T1 is set to, by the temperature in chemical vapor deposition process（Maximum temperature in chemical vapor deposition process）It is set to
T2, and handled at a temperature of T1 ＞ T2.
[5] active material for non-aqueous electrolyte secondary batteries of the as described in [4], wherein the coated particle with carbon coating
BET specific surface area be 0.2-30m2/g。
[6] lithium rechargeable batteries, it has the negative pole containing the negative electrode active material described in [4] or [5].
[7] electrochemical capacitors, it has the negative pole containing the negative electrode active material described in [4] or [5].
Invention effect
, can by the way that the coated particle obtained in the present invention is used as into anode for nonaqueous electrolyte secondary battery active material
It is high to obtain first efficiency for charge-discharge, high power capacity and excellent rechargeable nonaqueous electrolytic battery in terms of cycle characteristics.In addition, just make
Make easy for method, be especially suitable for plant-scale production.
Brief description of the drawings
[Fig. 1] is the X-ray diffraction of the coated particle obtained in embodiment 1,3（Cu-Kα）In, near 2 θ=28.4 °
Curve map.
[Fig. 2] is the X-ray diffraction of the coated particle obtained in example 2（Cu-Kα）In, the song near 2 θ=28.4 °
Line chart.
[Fig. 3] be comparative example 1,（Embodiment 1）The X-ray diffraction of the coated particle of middle acquisition（Cu-Kα）In, 2 θ=
Curve map near 28.4 °.
[Fig. 4] is the X-ray diffraction of the coated particle obtained in comparative example 2（Cu-Kα）In, the song near 2 θ=28.4 °
Line chart.
Specific embodiment
Hereinafter, the present invention is described in detail.
The manufacture method of the present invention, it is to be used, sharp as anode for nonaqueous electrolyte secondary battery active material
Use chemical vapor deposition（CVD）The manufacture method for the coated particle with carbon coating for handling and obtaining.That is, silica will be selected from
Particle, the composite particles that there are nano silicon particles to be scattered in structure in Si oxide, and the particle of their hybrid particles exist
It is not passed through after being heat-treated under organic gas, the particle after thus obtained heat treatment is changed in organic gas
Learn vapour deposition（CVD）The rechargeable nonaqueous electrolytic battery that coated particle with carbon coating obtained from processing is formed is used negative
The manufacture method of pole active material, it is characterized as the temperature of above-mentioned heat treatment（Maximum temperature in heat treatment）T1 is set to, will
Temperature in chemical vapor deposition（Maximum temperature in chemical vapor deposition process）It is set to T2, and T1 ＞ T2 manufacture method.
[selected from silicon oxide particle, have nano silicon particles be scattered in structure in Si oxide composite particles and they
Hybrid particles particle]
As chemical vapor deposition（CVD）The feed particles of before processing, following particles can be enumerated.
（1）Silicon oxide particle
Silica in the present invention is the general name of amorphous Si oxide.Silica before disproportionation is with formula SiOx（0 ＜
X≤2, preferably 0.8≤x ＜ 1.1）Represent.The silicon monoxide gas that the mixture of silica and metallic silicon is heated and generated
Cooling, precipitation can obtain silica.
（2）The composite particles for the structure being scattered in nano silicon particles in Si oxide
The side that the composite particles can be burnt till for example, by the mixture for being obtained by mixing the particulate of silicon and silicon systems compound
Method, or will be with above-mentioned（1）Formula SiOxSilicon oxide particle before the disproportionation of expression in the inert nonoxidizing atmosphere such as argon, with
More than 400 DEG C, preferably 800-1100 DEG C of temperature is heat-treated and carries out disproportionation to obtain.Particularly because pass through
The crystallite of the silicon for the material that the method for the latter obtains is dispersed, so being preferable.Using above-mentioned disproportionation, silicon can be received
The size of rice grain is changed into 1-100nm.On the silicon in the particle for the structure being scattered in nano silicon particles in Si oxide
Oxide, preferably silica, more preferably silica.In addition, confirm the nano particle of silicon using transmission electron microscope（It is brilliant
Body）It is scattered in unformed silica.
Anticathode X-ray diffraction is being used as using copper（Cu-Kα）In, by observation in belonging to be near 2 θ=28.4 °
The Si of the heart（111）Diffraction maximum, the composite particles of structure that there are nano silicon particles to be scattered in Si oxide can be confirmed.Separately
Outside, based on the width of the diffracted ray of diffraction maximum, the particle diameter of the crystal for the silicon tried to achieve according to Scherrer formula is preferably 1-
500nm, more preferably 1-100nm, more preferably 2-20nm.If the size of silicon grain is less than 1nm, discharge and recharge be present
The situation that capacity diminishes；If on the contrary, be more than 500nm, dilation during discharge and recharge becomes big, worries that cycle performance reduces.In addition,
The size of the particulate of silicon can be measured using transmission electron microscope photo.
Chemical vapor deposition（CVD）The average grain diameter of the feed particles of before processing is preferably 0.1-50 μm, and lower limit is more preferably
For more than 0.2 μm, further preferred more than 0.5 μm.The upper limit is more preferably less than 30 μm, further preferred less than 20 μm.In addition,
Average grain diameter in the present invention can represent by using the weight average particle diameter in the particle size distribution of laser diffractometry.
Chemical vapor deposition（CVD）The BET specific surface area of before processing is preferably 0.5-100m2/ g, more preferably 1-20m2/
g.In addition, the BET specific surface area in the present invention is to utilize to pass through N2Value during the BET1 points method measure of gas absorption amount evaluation.
[chemical vapor deposition（CVD）The heat treatment of before processing]
In chemical vapor deposition（CVD）In the heat treatment of before processing, be not passed through oxidizing gas carry out heat treatment be weight
Want.The inert gases such as argon are being passed through for example, having（Normal pressure）Or under decompression, the side that is preferably carried out under 50Pa-30000Pa decompression
Method.But if at a high temperature of more than 1100 DEG C, and if being heat-treated under reduced pressure, worry to occur silicon with
Silicon dioxde reaction, distillation.When being passed through inert gas, in order to eliminate remaining micro oxygen in atmosphere, have hydrogen or not
The method for carrying out the organic gas minipool of carbon CVD degree and being passed through.
[chemical vapor deposition（CVD）Processing]
By being continually fed into organic gas, chemical vapor deposition is carried out in organic gas（CVD）Processing.As with
Make the organic matter of the raw material of the organic gas in the generation present invention, especially selection can be under non-oxidizing atmosphere at above-mentioned heat
Thermally decomposed at a temperature of reason and generate carbon（Graphite）Material, such as methane, ethane, ethene, acetylene, propane, butane, penta can be enumerated
The single hydrocarbon such as alkane, iso-butane, hexane or its mixture；Benzene,toluene,xylene, styrene, ethylo benzene, diphenyl methane,
The aromatic hydrocarbon of the ring of one ring such as naphthalene, phenol, cresols, nitrobenzene, chlorobenzene, indenes, benzofuran, pyridine, anthracene, phenanthrene-three or they
Mixture.In addition, the light petrol obtained in tar distillation process, creasote, carbolineum, naphtha-cracked tar etc. can individually or make
Used for mixture.
In the present invention, by the temperature of above-mentioned heat treatment（Maximum temperature in heat treatment）It is set to T1, and by chemical gaseous phase
Temperature in deposition processes（Maximum temperature in chemical vapor deposition process）T2, and T1 ＞ T2 are set to, i.e., in chemical vapor deposition
Product（CVD）It is heat-treated in advance before processing, chemical vapor deposition is carried out with the temperature lower than the heat treatment（CVD）Processing is
Important.In T1=T2, it is impossible to the purpose of the present invention is realized, if T1 ＜ T2, in the case where T2 is high temperature, appropriate
At a temperature of carry out chemical vapor deposition（CVD）Handle and the state change of caused carbon coating, worry is used as negative electrode active material
And characteristic is damaged in the case of use.
In addition, although T2 is the temperature in chemical vapor deposition process（Maximum temperature in chemical vapor deposition process）,
But in the present invention, " chemical vapor deposition process " refers to while organic gas is passed through, be heat-treated.Therefore, even
It is continuous to carry out chemical vapor deposition（CVD）The heat treatment of before processing and chemical vapor deposition（CVD）In the case of processing, it is being passed through
It is " chemical vapor deposition before machine thing gas（CVD）The heat treatment of before processing ", it is passed through organic gas and is changed into " chemical gaseous phase afterwards
Deposition（CVD）Processing ".
If using said temperature, the condition handled is not particularly limited, but preferably " chemical vapor deposition（CVD）Place
Heat treatment before reason "（T1）Temperature be 900-1300 DEG C, more preferably 1000-1200 DEG C.If treatment temperature is more than 1300
DEG C, then worry capacity dramatic decrease；If it is in the temperature province less than 1300 DEG C, by making silica qi in treatment temperature
Change, nano silicon particles is become greatly to improve first efficiency for charge-discharge.Processing time is preferably 1-20 hours, and more preferably 2-3 is small
When.Chemical vapor deposition（CVD）Treatment temperature T2 suitably selects according to the species of organic gas.In addition, T1 ＞ will be met
T2 is set to condition, is suitably selected in the range of preferred 850-1250 DEG C, more preferably 950-1150 DEG C.Chemical vapor deposition
（CVD）Processing time is suitably selected according to the species of gas, the carbon amounts of needs.
Carbon amount of coating is not particularly limited, but overall relative to the coated particle being coated to through carbon, preferably 0.3-40 matter
Measure %, more preferably 0.5-30 mass %.When carbon amount of coating is less than 0.3 mass %, worry can not maintain sufficient electric conductivity, make
For result, when anode for nonaqueous electrolyte secondary battery active material is made, cycle performance reduction be present.On the contrary,
Even if carbon amount of coating not only cannot see that the raising of effect, on the contrary the ratio of graphite shared in negative material more than 40 mass %
Become big, in the case of as anode for nonaqueous electrolyte secondary battery active material, charge/discharge capacity reduction be present.
[the coated particle with carbon coating]
The coated particle with carbon coating obtained as described above is preferably to be scattered in silica with nano silicon particles
There is the coated particle of carbon coating on the surface of the composite particles of structure in compound.In addition, in chemical vapor deposition（CVD）Place
Feed particles before reason have（2）In the case that nano silicon particles are scattered in the composite particles of the structure in Si oxide, it can obtain
Obtain the coated particle with carbon coating on the surface of the composite particles for the structure that Si oxide is scattered in nano silicon particles.
In addition,（1）In the case of silicon oxide particle, " chemical vapor deposition is utilized（CVD）The heat treatment of before processing " or " chemical gaseous phase
Deposition（CVD）The heat treatment of before processing " and " chemical vapor deposition（CVD）Processing ", by the disproportionation of silica, becomes to have
There are the composite particles for the structure that nano silicon particles are scattered in Si oxide, can obtain and be scattered in silicon with nano silicon particles
There is the coated particle of carbon coating on the surface of the composite particles of structure in oxide.Above-mentioned composite particles preferably 0 ＜ oxygen/silicon
（Mol ratio）＜ 1.0.
The average grain diameter of coated particle with carbon coating is preferably 0.1-20 μm, and lower limit is more preferably more than 0.5 μm, enters
Preferably more than 1 μm of one step.More preferably less than 20 μm, further preferred less than 15 μm of the upper limit.In addition, in the present invention, average grain
Footpath can represent by using the weight average particle diameter in the particle size distribution measuring of laser diffractometry.
The BET specific surface area of coated particle with carbon coating is preferably 0.2-30m2/ g, more preferably 0.5-20m2/ g, enters
The preferred 0.5-8m of one step2/ g, particularly preferred 0.5-4.0m2/g.If more than 30m2/ g, then with the contact area increase of electrolyte, carry on a shoulder pole
The heart promotes the decomposition reaction of electrolyte.Using the manufacture method of the present invention, coated with above-mentioned BET specific surface area can be obtained
Grain.
[anode for nonaqueous electrolyte secondary battery chemical substance]
Coated particle with above-mentioned carbon coating is used as anode for nonaqueous electrolyte secondary battery active material by the present invention.
Thus, high first efficiency for charge-discharge, high power capacity and excellent rechargeable nonaqueous electrolytic battery in terms of cycle characteristics can be obtained.
[negative electrode material for nonaqueous electrode secondary battery]
The negative electrode material for nonaqueous electrode secondary battery of the present invention contains the coated particle with above-mentioned carbon coating.It is excellent
The negative pole of the coated particle of choosing（Solid portion in negative material）In content be 20-95 mass %, more preferred 30-90 matter
Measure %.
In negative electrode material for nonaqueous electrode secondary battery, the conductive agents such as carbon, graphite can be added.Even in the situation
Under, the species of conductive agent is also not particularly limited, as long as do not cause the electronics for decomposing or going bad to pass in the battery formed
The material for the property led, metallic particles or the metallic fibers or day such as Al, Ti, Fe, Ni, Cu, Zn, Ag, Sn, Si specifically can be used
Right graphite, Delanium, various coke granules, mesocarbon, gas-phase growth of carbon fibre, pitch-based carbon fiber, PAN systems carbon are fine
The graphite of dimension, various resin sintered bodies etc..
[negative pole]
As negative pole（Formed body）Preparation method, following methods can be enumerated.To above-mentioned coated particle and as needed
1-METHYLPYRROLIDONE or water equal solvent are mixed into other additives such as conductive agent, binding agent, is allowed to be changed into the mixed of pasty state
Compound, the mixture is coated on the sheet material of collector.In the case, as collector, as long as being copper foil, nickel foil etc.
The material used usually as the collector of negative pole, it becomes possible in the case where no thickness is particularly limited to what is be surface-treated
Use.In addition, the manufacturing process that the mixture is shaped to sheet is not particularly limited, known method can be used.
[lithium rechargeable battery]
Lithium rechargeable battery is characterised by using the material such as above-mentioned negative pole, other positive poles, negative pole, electrolyte, barrier film
Material and cell shapes etc. are not particularly limited known to can be used.For example, as positive active material, LiCoO can be used2、
LiNiO2、LiMn2O4、V2O5、MnO2、TiS2、MoS2Oxide, lithium ion and chalcogen compound Deng transition metal etc..Make
, can be by carbon as nonaqueous solvents for electrolyte, such as the usable non-aqueous solution containing lithium salts such as lithium hexafluoro phosphate, lithium perchlorates
One kind of the sub- propyl ester of acid, ethylene carbonate, diethyl carbonate, dimethoxy-ethane, gamma-butyrolacton, 2- methyltetrahydrofurans etc.
Or it is used in combination.Alternatively, it is also possible to use various non-water system electrolyte or solid electrolyte in addition.
[electrochemical capacitor]
Electrochemical capacitor is characterised by material and electricity using above-mentioned negative material, other electrolyte, barrier film etc.
Container shapes etc. are unrestricted.For example, it can be used as electrolyte containing lithium hexafluoro phosphate, lithium perchlorate, lithium fluoroborate, hexafluoro
The non-aqueous solution of the lithium salts such as arsenic acid lithium, can be by propylene carbonate, ethylene carbonate, dimethyl carbonate, carbonic acid as nonaqueous solvents
The one or more of diethylester, dimethoxy-ethane, gamma-butyrolacton, 2- methyltetrahydrofurans etc. are applied in combination.In addition,
Various non-water system electrolyte or solid electrolyte in addition can also be used.
Embodiment
Embodiment and comparative example are shown below, specifically illustrates the present invention, but the present invention is not limited to following implementation
Example.
Embodiment 1
It is 5 μm by average grain diameter, BET specific surface area 3.5m2/ g silica：SiOx（x=0.92）300g loads interval
In formula heating furnace.After being depressurized by oily rotary vacuum pump in stove, argon is passed through with 0.1L/min, recovers pressure.While press
Argon is passed through as former state, while with 200 DEG C/hr（Hour, similarly hereinafter）1150 DEG C will be warming up in stove, be so kept for 3 hours.After cooling
Take out, confirm physical property, although size distribution does not change, BET specific surface area is reduced to 1.9m2/g.By 100g
The particle loads in batch kiln, by oily rotary vacuum pump while will be depressurized in stove, while with 200 DEG C/hr by stove
1000 DEG C are inside warming up to, makes CH after reaching 1000 DEG C4Gas is flowed into 0.3NL/min, carries out the carbon coating treatment of 20 hours.This
When degree of decompression be 800Pa.Cool after processing, obtain 105g black particles.The black particle of acquisition is the μ of average grain diameter 5.2
M, BET specific surface area 2.0m2/ g, the conductive particle that the carbon amount of coating relative to black particle is 4.8 mass %.
＜ cell evaluations ＞
Then, by the following method, the battery that the coated particle of acquisition is used as to negative electrode active material is evaluated.
It is following to make negative pole：By the mass % of particle 45 and Delanium of acquisition（10 μm of average grain diameter）45 mass %, polyamides
The mass % of imines 10 is mixed, and is further added 1-METHYLPYRROLIDONE and is made into slurry, the slurry is coated on into 12 μm of thickness
It is using roll squeezer that electrode is compressing after 80 DEG C are dried 1 hour on copper foil, the electrode is subjected to vacuum at 350 DEG C and done
After dry 1 hour, 2cm is stamped into2, negative pole is made.Here, in order to evaluate the charge-discharge characteristic of the negative pole of acquisition, lithium paper tinsel is used as
To electrode, ethylene carbonate and carbonic acid are dissolved in 1 mole/L concentration using using as the lithium hexafluoro phosphate of nonaqueous electrolyte
The 1/1 of diethylester（Volume ratio）Non-aqueous electrolytic solution in mixed liquor, made using 30 μm of polyethylene microporous film of thickness
For barrier film, evaluation lithium rechargeable battery is made.
After the lithium rechargeable battery of making is placed into an evening at room temperature, using charging/discharging of secondary cell experimental provision
（（Strain）Na ガ ノ systems）, with 0.5mA/cm2Constant current charged, until test battery voltage reach 0V, reaching
After 0V, reduce electric current and charged, to keep cell voltage as 0V.Then, it is less than 40 μ A/cm in current value2When stop fill
Electricity.Electric discharge is with 0.5mA/cm2Constant current carry out, when cell voltage reaches 2.0V stop electric discharge, obtain discharge capacity.Weight
Multiple above charge and discharge electric test, carry out the charge and discharge electric test after 50 circulations of evaluation lithium rechargeable battery.As a result, confirm
Primary charging capacity is 2291mAh/g, and initial discharge capacity is 1811mAh/g, first efficiency for charge-discharge 79%, follows the 50th time
The high power capacity of the discharge capacity sustainment rate 92.3% of ring, and lithium ion excellent in terms of first efficiency for charge-discharge and cycle performance
Secondary cell.
Embodiment 2
The SiO that will be heat-treated in embodiment 1xParticle 100g loads in batch kiln.Rotated using oil
Formula vavuum pump in stove while will depressurize, while 1100 DEG C will be heated in stove with 200 DEG C/hr, with 0.3NL/ since 1000 DEG C
Min is passed through CH4Gas, while it is warming up to 1100 DEG C with 30 DEG C/hr programming rate.At 1100 DEG C, it is passed through with 0.3NL/min
CH4Kept for 10 hours in the state of gas, carry out carbon coating treatment.Cool after processing, obtain 105.4g black particles.Obtained
Black particle be 5.3 μm of average grain diameter, BET specific surface area 3.2m2/ g, relative to the carbon amount of coating 5.1 of black particle
Quality % conductive particle.
Embodiment 3
The SiO that will be heat-treated in embodiment 1xParticle 100g loads in batch kiln.Rotated by oil
Formula vavuum pump while will be warming up to 950 DEG C in stove with 200 DEG C/hr, when reaching 950 DEG C, will pass through gas while will be depressurized in stove
The gas that changing device makes toluene gasify is passed through with 0.3g/min, is kept for 3 hours, carries out carbon coating treatment.Cool after processing, obtain
105.7g black particle.The black particle obtained is 5.3 μm of average grain diameter, BET specific surface area 1.8m2/ g, relative to black
The carbon amount of coating of coloured particles is 5.4 mass % conductive particle.
Comparative example 1
The SiO that will be used in embodiment 1xParticle 100g loads in batch kiln without heat treatment.Using oil
Rotary vacuum pump while will be warming up to 1000 DEG C in stove with 200 DEG C/hr, makes CH while will be depressurized in stove4Gas is with 0.3NL/
Min is flowed into, and carries out 20 hours carbon coating treatments.Cool after processing, obtain 105.1g black particles.The black particle obtained
For 5.2 μm of average grain diameter, conductive particle that the carbon amount of coating relative to black particle is 4.9 mass %, BET specific surface area is
4.7m2/g。
Then negative pole is made in the same manner as in Example 1, carries out cell evaluation.The result is that primary charging capacity is
2271mAh/g, initial discharge capacity are 1698mAh/g, and first efficiency for charge-discharge is 75%, the discharge capacity dimension of the 50th circulation
Holdup is 93.1%.Compared with embodiment, it is clear that confirm it for the poor lithium ion secondary electricity of first efficiency for charge-discharge
Pond.
Comparative example 2
The SiO that will be used in embodiment 1xParticle 100g loads in batch kiln.It is while rotary true using oil
Empty pump will depressurize in stove, while will be warming up to 1000 DEG C in stove with 200 DEG C/hr, make CH4Gas is flowed into 0.3NL/min, is carried out
The carbon coating treatment of 20 hours.Afterwards, CH is stopped4After gas, 1150 DEG C are warming up to 200 DEG C/hr, is kept for 3 hours.Processing
After cool, obtain 105.5g black particles.The black particle obtained is 5.2 μm of average grain diameter, relative to black particle
Carbon amount of coating is 5.2 mass % conductive particle, but BET specific surface area is 9.2m2/ g high level.
Then negative pole is made in the same manner as in Example 1, carries out cell evaluation.The result is that primary charging capacity is
2281mAh/g, initial discharge capacity are 1802mAh/g, and first efficiency for charge-discharge is 79%, the discharge capacity dimension of the 50th circulation
Holdup is 82.5%.Compared with embodiment, it is clear that confirm it for the poor lithium rechargeable battery of cycle characteristics.In table 1
Show T1（℃）：The temperature of heat treatment（Maximum temperature in heat treatment）、T2（℃）：Temperature in chemical vapor deposition process
（Maximum temperature in chemical vapor deposition process）, heat treatment and chemical vapor deposition process condition.Evaluation result is shown in
In table 2.
Table 1
Table 2
The X-ray diffraction of the coated particle obtained in embodiment 1-3, comparative example 1-2 is shown in figures 1-4（Cu-K
α）In, the curve map near 2 θ=28.4 °.By the result understand can to realize simultaneously in embodiment 1-3 appropriate CVD temperature and
It can obtain the disproportionation of high initial efficiency characteristic.In addition, the initial efficiency of the battery of the coated particle of embodiment has been used with following
Excellent of both ring property.
Claims (5)
1. the manufacture method for the anode for nonaqueous electrolyte secondary battery active material being made up of the coated particle with carbon coating,
It is by selected from silicon oxide particle, composite particles and their mixing that there are nano silicon particles to be scattered in structure in Si oxide
The particle of particle is not after being passed through and being heat-treated under organic gas, to the heat treated particulate that is obtained in organic gas
Carry out chemical vapor deposition (CVD) processing, it is characterised in that the BET specific surface area of the coated particle is 0.5~4.0m2/ g,
The temperature T1 of above-mentioned heat treatment is 900~1200 DEG C, and the temperature T2 in chemical vapor deposition process is 850~1150 DEG C, above-mentioned
T1 and T2 relation is T1 ＞ T2.
2. manufacture method as claimed in claim 1, wherein the coated particle is to be scattered in silica with nano silicon particles
There is the coated particle of carbon coating on the surface of the composite particles of structure in compound.
3. the anode for nonaqueous electrolyte secondary battery active material being made up of the coated particle with carbon coating, it passes through as follows
Method and obtain：By selected from silicon oxide particle, have nano silicon particles be scattered in structure in Si oxide composite particles and
The particle of their hybrid particles exists after not being passed through and being heat-treated under organic gas to particle after the heat treatment that is obtained
When chemical vapor deposition (CVD) processing is carried out in organic gas, it is 900~1200 DEG C, changes in the temperature T1 of above-mentioned heat treatment
Carried out at a temperature of temperature T2 in vapour deposition processing is 850~1150 DEG C and above-mentioned T1 and T2 relation is T1 ＞ T2
Processing,
The BET specific surface area of the coated particle is 0.5~4.0m2/g。
4. lithium rechargeable battery, it has the negative pole containing the negative electrode active material described in claim 3.
5. electrochemical capacitor, it has the negative pole containing the negative electrode active material described in claim 3.
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| JP6403540B2 (en) * | 2014-10-30 | 2018-10-10 | 信越化学工業株式会社 | Negative electrode material for lithium ion secondary battery and method for producing the same, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
| KR102591996B1 (en) * | 2015-07-31 | 2023-10-20 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Negative electrode material for lithium ion secondary battery, manufacturing method thereof, and lithium ion secondary battery |
| CN107317006A (en) * | 2017-06-21 | 2017-11-03 | 中国科学院宁波材料技术与工程研究所 | Aoxidize silicon substrate carbon compound cathode materials, its preparation method and lithium ion battery |
| JP6592156B2 (en) * | 2018-09-11 | 2019-10-16 | 信越化学工業株式会社 | Negative electrode material for lithium ion secondary battery and method for producing the same, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
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| CN101847710A (en) * | 2009-03-25 | 2010-09-29 | 信越化学工业株式会社 | Negative electrode material for nonaqueous electrolyte secondary battery, making method and lithium ion secondary battery |
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