WO2011010430A1 - 堆積量測定装置、堆積量測定方法及び電気化学素子用電極の製造方法 - Google Patents
堆積量測定装置、堆積量測定方法及び電気化学素子用電極の製造方法 Download PDFInfo
- Publication number
- WO2011010430A1 WO2011010430A1 PCT/JP2010/004365 JP2010004365W WO2011010430A1 WO 2011010430 A1 WO2011010430 A1 WO 2011010430A1 JP 2010004365 W JP2010004365 W JP 2010004365W WO 2011010430 A1 WO2011010430 A1 WO 2011010430A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ray
- substrate
- lithium
- deposition
- backscattering
- Prior art date
Links
- 230000008021 deposition Effects 0.000 title claims abstract description 93
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims description 49
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 194
- 239000000758 substrate Substances 0.000 claims abstract description 187
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 182
- 238000000151 deposition Methods 0.000 claims abstract description 112
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 230000005250 beta ray Effects 0.000 claims description 231
- 230000009467 reduction Effects 0.000 claims description 61
- 238000005259 measurement Methods 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 36
- 238000001704 evaporation Methods 0.000 claims description 32
- 230000008020 evaporation Effects 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 24
- 230000007423 decrease Effects 0.000 claims description 21
- 230000001678 irradiating effect Effects 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 230000003685 thermal hair damage Effects 0.000 claims description 5
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 239000000523 sample Substances 0.000 description 30
- 239000011149 active material Substances 0.000 description 22
- 238000007740 vapor deposition Methods 0.000 description 21
- 238000009792 diffusion process Methods 0.000 description 14
- 239000010409 thin film Substances 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 230000002427 irreversible effect Effects 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000001771 vacuum deposition Methods 0.000 description 9
- 238000005137 deposition process Methods 0.000 description 8
- 230000007246 mechanism Effects 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- 239000003507 refrigerant Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000469 dry deposition Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
Images
Classifications
-
- 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
- H01M4/139—Processes of manufacture
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
- C23C14/542—Controlling the film thickness or evaporation rate
- C23C14/545—Controlling the film thickness or evaporation rate using measurement on deposited material
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
- C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
-
- 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
-
- 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
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0423—Physical vapour deposition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/13—Energy storage using capacitors
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a deposition amount measuring apparatus, a deposition amount measuring method, and a method for manufacturing an electrode for an electrochemical element.
- the positive and negative electrodes of the lithium secondary battery are charged and discharged by inserting and extracting lithium.
- the occlusion and release are not completely reversible reactions.
- a large proportion of lithium occluded in the negative electrode during initial charging may not be released from the negative electrode during discharge.
- This capacity difference between charge and discharge caused by the lithium that is not released is called irreversible capacity.
- the irreversible capacity at the time of initial charge is large, the utilization efficiency of lithium contained in the positive electrode is lowered. This hinders improvement in charge / discharge capacity.
- the amount of lithium deposited When reducing the irreversible capacity by vapor deposition, it is desirable to control the amount of lithium deposited so that the initial irreversible capacity becomes equal to zero. If the amount of deposition is too small, the loss of charge / discharge capacity due to the initial irreversible capacity cannot be reduced sufficiently. If the amount of deposition is too large, lithium may remain on the surface of the negative electrode active material layer without diffusing into the negative electrode active material layer. The lithium remaining on the surface of the negative electrode active material layer causes a decrease in charge / discharge characteristics.
- the present invention provides a novel technique for achieving this object.
- the present invention A deposition step of depositing lithium on a substrate provided with a layer that forms a compound with lithium; Prior to the deposition step, the substrate is irradiated with a first ⁇ ray using a first ⁇ ray source and a second ⁇ ray using a second ⁇ ray source containing a nuclide different from the nuclide of the first ⁇ ray source.
- a first ⁇ -ray irradiation step to perform A first measurement step of measuring backscattering of the first ⁇ -ray and the second ⁇ -ray from the substrate irradiated in the first ⁇ -ray irradiation step; A second ⁇ -ray irradiation step of irradiating the substrate with the first ⁇ -ray and the second ⁇ -ray after the deposition step; A second measurement step of measuring backscattering of the first ⁇ -ray and the second ⁇ -ray from the substrate irradiated in the second ⁇ -ray irradiation step; Using the result obtained in the first measurement step and the result obtained in the second measurement step, a reduction amount of the back scattering of the first ⁇ ray and a reduction amount of the back scattering of the second ⁇ ray are calculated.
- the manufacturing method of the electrode for electrochemical elements containing is provided.
- the present invention provides: An apparatus for measuring the amount of lithium deposited on a substrate provided with a layer that forms a compound with lithium, A first ⁇ -ray source for irradiating the substrate with a first ⁇ -ray; A second ⁇ -ray source having a nuclide different from the nuclide of the first ⁇ -ray source and irradiating the substrate with a second ⁇ -ray; A ⁇ -ray detector for measuring backscattering from the substrate of the first ⁇ -ray and the second ⁇ -ray irradiated from the first ⁇ -ray source and the second ⁇ -ray source; A deposition amount measuring apparatus is provided.
- the present invention provides: A deposition step of depositing lithium on a substrate provided with a layer that forms a compound with lithium; Prior to the deposition step, the substrate is irradiated with a first ⁇ ray using a first ⁇ ray source and a second ⁇ ray using a second ⁇ ray source having a nuclide different from the nuclide of the first ⁇ ray source.
- a first ⁇ -ray irradiation step A first measurement step of measuring backscattering of the first ⁇ -ray and the second ⁇ -ray from the substrate irradiated in the first ⁇ -ray irradiation step; A second ⁇ -ray irradiation step of irradiating the substrate with the first ⁇ -ray and the second ⁇ -ray after the deposition step; A second measurement step of measuring backscattering of the first ⁇ -ray and the second ⁇ -ray from the substrate irradiated in the second ⁇ -ray irradiation step; Using the result obtained in the first measurement step and the result obtained in the second measurement step, a reduction amount of the back scattering of the first ⁇ ray and a reduction amount of the back scattering of the second ⁇ ray are calculated. Calculation process; A deposition amount measuring method is provided.
- the present invention provides: Preparing a substrate provided with a layer forming a compound with lithium; While adjusting the temperature of the substrate to a temperature between the first threshold temperature and the second threshold temperature so that lithium deposited on the substrate can diffuse into the substrate and suppress thermal damage of the substrate.
- a ⁇ -ray irradiation step of irradiating the substrate with ⁇ -rays before the deposition step A measurement step of measuring backscattering of the ⁇ rays from the substrate irradiated in the ⁇ -ray irradiation step; A second ⁇ -ray irradiation step of irradiating the substrate with the ⁇ -rays after the deposition step; A second measurement step of measuring backscattering of the ⁇ -rays from the substrate irradiated in the second ⁇ -ray irradiation step; Using the result obtained in the first measurement step and the result obtained in the second measurement step, a calculation step for calculating a reduction amount of the backscattering of the ⁇ ray, A control step of controlling the deposition step in accordance with the amount of decrease in the beta rays; The manufacturing method of the electrode for electrochemical elements containing is provided.
- two types of ⁇ -ray sources are used.
- (i) whether lithium is sufficiently diffused in the layer forming the compound with lithium, and (ii) the amount of lithium deposited can know.
- the control process can be performed so that the deposition amount approaches the target value. Similarly, the control process can be performed to ensure that lithium diffuses into the substrate. As a result, an electrode for an electrochemical element that can reliably reduce the initial irreversible capacity can be produced.
- the amount of lithium deposition can be accurately controlled even when one type of ⁇ -ray source is used.
- the temperature of the substrate is adjusted to a temperature between the first threshold temperature and the second threshold temperature so that lithium deposited on the substrate can diffuse into the substrate and thermal damage to the substrate is suppressed. While, lithium is deposited on the substrate. In this case, it is sufficient to measure only the amount of deposited lithium by ⁇ -ray backscattering. That is, the control process is performed so that the amount of lithium deposition approaches the target value.
- the electrode for electrochemical elements which can reduce an initial irreversible capacity
- FIG. 1 Schematic structural diagram of a vacuum deposition apparatus that can be used in the practice of the present invention
- Flow chart of vapor deposition control in an embodiment of the present invention Schematic showing backscattering of high energy ⁇ rays (first ⁇ rays)
- Correlation diagram showing the relationship between lithium diffusion and ⁇ -ray backscattering
- the backscattering probability when the surface of a layer is irradiated with ⁇ -rays is almost proportional to the logarithm of the atomic number of the substance constituting the layer. In the case of a compound, it is approximately proportional to the logarithm of the mass average of the atomic numbers of the elements contained in the layer. Since ⁇ -rays are not easily scattered by light elements, when lithium is contained in an active material layer such as a silicon thin film (when diffused), the back-scattering probability (backscattering yield) of ⁇ -rays decreases.
- the ⁇ -ray backscattering probability is almost proportional to the amount of lithium contained in the active material layer. Then decrease. Specifically, as shown in state 2 of FIG. 5, when lithium does not remain in the form of a thin film on the surface of the layer and lithium is diffused inside the layer, the backscattering probability is included in the layer. It decreases almost in proportion to the amount of lithium. This principle is independent of ⁇ -ray energy. Therefore, as shown in graphs 3 and 4 in FIG. 5, the profile of the backscattering probability of the high energy ⁇ ray with respect to the amount of deposited lithium substantially matches that of the low energy ⁇ ray.
- the ⁇ -ray backscattering probability is a little more complicated when the composition of the layer is not uniform.
- state 1 of FIG. 5 a case where light elements are unevenly distributed near the surface of the layer, in other words, a case where lithium is deposited on the surface of the layer in the form of a thin film is considered.
- graphs 1 and 2 in FIG. 5 the backscattering probability of high energy ⁇ -rays and the backscattering probability of low energy ⁇ -rays greatly decrease depending on the amount of lithium deposited.
- the profile of the backscattering probability of high energy ⁇ rays does not match the profile of the backscattering probability of low energy ⁇ rays.
- the low-energy ⁇ -ray backscattering occurs in the vicinity of the surface of the layer, and therefore the low-energy ⁇ -ray backscattering probability is greatly reduced even if the amount of lithium deposition is relatively small.
- the backscattering probability of the high energy ⁇ -ray is lower than that of the low energy ⁇ -ray. Decrease gradually according to the amount of deposition. That is, when lithium is unevenly distributed near the surface, the reduction rate of the backscattering probability of low energy ⁇ rays is larger than the reduction rate of the backscattering probability of high energy ⁇ rays.
- 147 Pm that emits 0.224 MeV ⁇ -ray is used as the nuclide of the high energy ⁇ -ray (first ⁇ -ray), and 0 nuclides of the low-energy ⁇ -ray (second ⁇ -ray) are used.
- 14 C that emits 156 MeV ⁇ -rays is used.
- a lithium deposition thickness of about 10 ⁇ m is sufficient to reduce the initial irreversible capacity, and the occlusion of lithium into the active material layer occurs within a range of several tens of ⁇ m from the surface. That is, it is only necessary to measure whether lithium is unevenly distributed on the surface or diffused inside in a region of about 10 ⁇ m from the surface.
- ⁇ -rays having a plurality of energies in the range of 0.1 to 0.3 MeV are used. It is suitable to use.
- those with a long half-life (1 year or more) and the lower limit quantity set by the Ionizing Radiation Hazard Prevention Regulation are 147 Pm and 14 C, so these are adopted as nuclides in this embodiment. is doing.
- 147 Pm and 14 C are not essential as nuclides for carrying out the present invention. Any nuclide can be used as long as it can emit ⁇ -rays having different energies.
- FIG. 1 shows a schematic view of a vacuum deposition apparatus that can be used in the practice of the present invention.
- the vacuum deposition apparatus 100 has not only a function of depositing a material on the substrate 4 but also a function as a deposition amount measuring apparatus that measures the deposition amount of the deposited material.
- a vacuum deposition apparatus 100 includes a vacuum chamber 1, a vacuum pump 2, an evaporation source 3, an unwinding roll 5, conveying rolls 6 a to 6 d, a can roll 7, and a winding roll 8. And a first ⁇ -ray backscattering detection probe 9a and a second ⁇ -ray backscattering detection probe 9b.
- the first ⁇ -ray backscattering detection probe 9a and the second ⁇ -ray backscattering detection probe 9b are simply referred to as “first probe 9a” and “second probe 9b”.
- the evaporation source 3 can be used to deposit lithium on the substrate 4.
- a metal crucible or the like that does not react with lithium is used for the evaporation source 3.
- a heating device such as a resistance heating device, an induction heating device, or an electron beam heating device
- the material (lithium) accommodated in the crucible of the evaporation source 3 can be evaporated.
- the apparatus 100 uses a resistance heating apparatus 14.
- vacuum deposition is employed as a method for depositing lithium on the substrate 4.
- other dry deposition methods such as sputtering can be employed.
- the vacuum deposition apparatus 100 further includes a controller 12.
- the controller 12 controls the first probe 9a, the second probe 9b, the resistance heating device 14, and the can roll 7.
- the substrate 4 on which lithium is to be deposited is prepared on the unwinding roll 5, and is guided to the winding roll 8 along the transport roll 6a, the transport roll 6b, the can roll 7, the transport roll 6c, and the transport roll 6d. .
- the unwinding roll 5, the conveying rolls 6a to 6d, the can roll 7 and the winding roll 8 constitute a conveying system for conveying the substrate 4.
- the substrate 4 is usually transported at a constant speed by a transport system. However, the conveyance speed of the substrate 4 can be controlled in order to adjust the deposition rate of lithium on the substrate 4.
- the evaporation source 3 is opposed to the substrate 4 stretched on the outer periphery of the can roll 7.
- the range where the evaporated material can reach straight is the deposition surface.
- the can roll 7 has a cylindrical shape.
- the can roll 7 is provided with a temperature adjusting mechanism 13 (built in).
- the temperature adjustment mechanism 13 is configured by, for example, a flow path for flowing a refrigerant or a heating medium.
- the temperature of the substrate 4 can be controlled by changing the flow rate and / or temperature of the refrigerant or the heating medium flowing inside the temperature adjusting mechanism 13. Water, hot water, oil or the like can be used as the refrigerant or the heating medium.
- a substrate in which an active material layer of an electrochemical element is formed on a current collector can be used.
- a substrate in which a layer of a material that forms a compound with lithium is provided on a current collector can be used.
- the substrate 4 may be a substrate in which a thin film of a substance capable of inserting and extracting lithium is formed on a current collector.
- a substrate in which a thin film containing silicon is formed on a current collector can be used.
- a foil made of a metal such as copper, copper alloy, aluminum, aluminum alloy, nickel, or nickel alloy can be used.
- the electrochemical element include a lithium secondary battery and a lithium ion capacitor.
- Each of the first probe 9a and the second probe 9b includes a sealed radiation source that emits ⁇ rays and a radiation detector that can detect ⁇ rays.
- the nuclides of the ⁇ -ray source any one that emits ⁇ -rays can be used.
- the first probe 9a has a radioactivity of 3.7 MBq of 147 Pm sealed radiation source (first ⁇ -ray source), and the second probe 9b has a radioactivity of 1.6 MBq of 14 C sealed radiation source (second ⁇ -ray source). ) Is used.
- Any radiation detector that can operate in vacuum and can detect ⁇ -rays can be used.
- the apparatus 100 uses a silicon PIN photodiode detector.
- FIG. 3 shows the steps to be executed by the controller 12.
- the degree of vacuum inside the vacuum chamber 1 is maintained at a degree of vacuum suitable for vapor deposition of lithium and measurement of ⁇ -ray backscattering yield, for example, 10 ⁇ 1 to 10 ⁇ 4 Pa.
- the vacuum should be kept approximately constant.
- a vacuum is not essential for the present invention, and the present invention can also be applied to lithium deposition in the atmosphere.
- a refrigerant or a heating medium is caused to flow through the temperature adjustment mechanism 13 provided in the can roll 7, and temperature control of the substrate 4 by the temperature adjustment mechanism 13 is started (step S1).
- the substrate 4 is caused to travel (step S2).
- the long substrate 4 unwound from the unwinding roll 5 is guided in the order of the transporting roll 6 a, the transporting roll 6 b, the can roll 7, the transporting roll 6 c, and the transporting roll 6 d, and finally wound up by the winding roll 8.
- step S3 The backscattering yield from the substrate 4 of the first ⁇ ray and the second ⁇ ray is measured (step S3). That is, the backscattering yield is measured for the substrate 4 before lithium deposition. Thereby, the backscattering yield when the amount of deposited lithium is zero is obtained for each of the first ⁇ ray and the second ⁇ ray.
- the backscattering yield is measured for the substrate 4 before lithium deposition, it is preferable to perform the measurement while the substrate 4 is running. This is because even if there is some variation in the backscattering yield in the plane of the substrate 4, the variation is averaged if the measurement is performed while running, and an accurate value can be easily obtained. In particular, when the surface of the substrate 4 is uneven or the substrate 4 does not have a uniform density in the plane, it is desirable to measure the backscattering yield while the substrate 4 is running.
- step S4 lithium metal is put into the evaporation source 3 as a material, and the temperature is raised by resistance heating to evaporate (step S4).
- the deposition rate is usually 1 to 1000 nm / second, and the deposition amount of lithium (thickness converted to a thin film) is 1 to 10 ⁇ m.
- the step of depositing lithium on the substrate 4 can be performed while the step of transporting the substrate 4 is performed. This method is excellent in productivity.
- the 2nd beta ray irradiation process mentioned later and the 2nd measurement process can be implemented, implementing a conveyance process and a deposition process.
- the temperature of the substrate 4 during vapor deposition varies depending on the balance between the heat of condensation of the deposited lithium metal and the radiation heat from the evaporation source 3 and the heat radiation to the can roll 7 in contact with the back surface of the substrate 4. It is possible to control the maximum temperature reached by the substrate 4 during vapor deposition by changing the temperature or flow rate of the refrigerant or heating medium flowing inside the can roll 7 (temperature adjusting mechanism 13). The actual maximum temperature of the substrate 4 can be confirmed from a decrease in the tensile strength of the thermolabel attached to the back surface or the metal foil used for the substrate 4.
- step S5 The backscattering yield from the substrate 4 of the first ⁇ ray and the second ⁇ ray is measured (step S5).
- the backscatter yield is expressed as a yield per unit time (for example, 1 second) (count per sec).
- the backscattering yield is measured while conveying the substrate 4. Therefore, the backscattering yield per unit time shows an average value for a certain region.
- the yield reduction rate (decrease amount) is calculated for each of the first ⁇ line and the second ⁇ line (step S6).
- the reduction rate can be calculated according to the following formula.
- step S7 it is determined whether or not the difference between the reduction rate of the backscattering yield of the first ⁇ ray and the reduction rate of the backscattering yield of the second ⁇ ray is within a predetermined range. If the difference in the reduction rate is within a predetermined range, it is determined that lithium is diffusing into the substrate 4, and the deposition is continued without changing the current deposition conditions.
- the “predetermined range” is a range in consideration of measurement errors. For example, when the difference in the reduction rate is within a range of ⁇ 3%, it can be determined that lithium is almost diffused in the substrate 4.
- step S8 the temperature control of the substrate 4 is performed (step S8). Specifically, the temperature of the refrigerant or the heating medium is increased. When the temperature of the refrigerant or the heating medium is increased, the temperature of the substrate 4 is increased, so that the diffusion of lithium into the substrate 4 is promoted. Thereby, the difference in the reduction rate is reduced. Thereafter, the process returns to step S5, and the backscattering yield measurement (step S6) and the reduction rate calculation (step S7) are performed again.
- step S9 it is next determined whether or not the reduction rate of the backscattering yield of the first ⁇ ray or the second ⁇ ray matches the target value (step S9). Precisely, it is determined whether the reduction rate is within the target range. If the reduction rate matches the target value (within the target range), it is determined that the amount of lithium deposition is appropriate, and the deposition continues without changing the current deposition conditions.
- step S10 evaporation rate control is performed (step S10). Specifically, when the rate of decrease is larger than the target value, the amount of deposited lithium is excessive, so the heating device 14 is controlled so that the evaporation rate of lithium from the evaporation source 3 is reduced (specifically, the current is reduced). cut back). When the decrease rate is smaller than the target value, the amount of lithium deposited is insufficient, and thus the heating device 14 is controlled so as to increase the evaporation rate of lithium from the evaporation source 3 (increase the current).
- the temperature control is performed so that the difference in the decrease rate of the ⁇ -ray backscattering yield falls within a predetermined range.
- the vapor deposition is performed so that the reduction rate of the backscattering yield of the first ⁇ ray or the second ⁇ ray matches the target value (contains within the target range).
- the deposition process is performed while the transport process is performed so that the deposited portion where lithium is deposited and the undeposited portion where lithium is not deposited are formed on the long substrate 4. .
- the calculation step calculates the reduction rate of the backscattering of the first ⁇ ray from the reduction amount of the backscattering of the first ⁇ ray, and calculates the reduction rate of the backscattering of the second ⁇ ray. Including calculating the reduction rate of 2 ⁇ backscattering.
- the control step it is determined whether or not the difference between the reduction rate of the backscattering of the first ⁇ ray and the reduction rate of the backscattering of the second ⁇ ray is within a predetermined range.
- the deposition process is controlled so as to increase the temperature.
- the reduction rate of the backscattering of the first ⁇ ray or the backscattering of the second ⁇ ray It is determined whether or not the reduction rate is within the target range, and if it is not within the target range, the deposition process is controlled so as to increase the deposition rate of lithium.
- the difference between the decrease rate of the backscattering yield of the first ⁇ ray and the decrease rate of the backscattering yield of the second ⁇ ray indicates the uneven distribution of lithium in the substrate 4, that is, the diffusion state of lithium into the substrate 4.
- the reduction rate of the backscattering yield of the first ⁇ ray and the reduction rate of the backscattering yield of the second ⁇ ray indicate the amount of lithium deposited, respectively. According to this embodiment, it is possible to deposit lithium on the substrate 4 while appropriately controlling the deposition of lithium and the diffusion of lithium into the substrate 4.
- Each process shown in FIG. 3 is automatically performed by the operation of the controller 12. That is, the controller 12 irradiates the first ⁇ ray and the second ⁇ ray on the substrate 4 before depositing lithium, and measures the first ⁇ ray backscattering and the second ⁇ ray backscattering so as to measure the first probe 9a. And the second probe 9b is controlled. Further, the controller 12 irradiates the substrate 4 after depositing lithium with the first ⁇ ray and the second ⁇ ray to measure the backscattering of the first ⁇ ray and the backscattering of the second ⁇ ray. 9a and the second probe 9b are controlled.
- the controller 12 calculates a reduction amount of the backscattering of the first ⁇ ray and a reduction amount of the backscattering of the second ⁇ ray before and after the deposition of lithium, respectively. Based on the calculation result, the controller 12 controls the subsequent deposition process. That is, the controller 12 determines whether the current deposition conditions (the temperature of the substrate 4 and the deposition rate of lithium) are appropriate using the calculation result. Current deposition conditions are maintained where appropriate. If not appropriate, the deposition conditions are corrected.
- the diffusion of lithium into the substrate 4 is appropriately controlled by controlling the temperature during vapor deposition.
- the step of transporting the substrate 4 includes transport of the substrate 4 along the cylindrical can roll 7. There is an area for depositing lithium where the substrate 4 is along the can roll 7.
- the step of controlling the deposition step includes temperature control of the can roll 7, specifically, temperature control of the substrate 4 by the temperature adjusting mechanism 13 provided in the can roll 7. That is, the temperature of the substrate 4 is adjusted by controlling the temperature of the can roll 7 so that the deposited lithium can diffuse into the substrate 4.
- the temperature of the substrate 4 can be adjusted in the region for depositing lithium, so that the responsiveness is excellent. Moreover, it can prevent reliably that the temperature of the board
- the temperature during vapor deposition is not sufficient for diffusion, it is also possible to appropriately control the diffusion of lithium into the substrate 4 by heating the substrate 4 using another heat source after vapor deposition.
- at least one of the transport roll 6c and the transport roll 6d disposed on the downstream side of the can roll 7 with respect to the transport direction of the substrate 4 may be configured as a heating roll.
- the “heating roll” is a roll having a function of heating the substrate 4.
- the step of transporting the substrate 4 includes transport of the substrate 4 along the heating roll, the substrate 4 is transported along the heating roll after passing through the region for depositing lithium. If the intensity of heating of the substrate 4 by the heating roll is adjusted, the diffusion of lithium into the substrate 4 can be promoted or suppressed.
- the step of controlling the deposition step includes temperature control of the heating roll.
- the method of positively heating the substrate 4 is effective when the distance between the substrate 4 and the evaporation source 3 is relatively long and the temperature of the substrate 4 does not rise sufficiently during vapor deposition.
- the deposition step includes evaporating lithium from the evaporation source 3 so that lithium is deposited on the substrate 4.
- the step of controlling the deposition step includes the evaporation rate control of the evaporation source 3.
- the evaporation rate of lithium from the evaporation source 3 is controlled by adjusting the intensity of heating of the evaporation source 3 by the heating device 14.
- the deposition rate of lithium is adjusted by controlling the evaporation source 3 so that the deposition amount of lithium approaches the target value. Thereby, the amount of lithium deposited on the substrate 4 can be adjusted.
- lithium can be deposited on the substrate 4 while monitoring the deposition amount with one ⁇ -ray source.
- the following preliminary experiment is performed to find a temperature condition (cooling or heating condition of the can roll 7) where lithium can surely diffuse inside the substrate 4.
- lithium is deposited on the substrate 4 under some cooling or heating conditions of the can roll 7.
- the reduction rate of the backscattering yield of the first ⁇ ray and the reduction rate of the backscattering yield of the second ⁇ ray are calculated and compared. If the reduction rates are almost the same, lithium is sufficiently diffused inside the substrate 4, and the cooling or heating conditions at that time are appropriate.
- the evaporation rate can be controlled according to the backscattering yield of ⁇ -ray with 147 Pm as a nuclide, and the amount of lithium deposited can be set to a predetermined amount. For example, when the decrease rate of the ⁇ -ray backscattering yield with 147 Pm as a nuclide is smaller than the target value, the temperature of the evaporation source 3 is increased to increase the evaporation rate of lithium. When the reduction rate of the backscattering yield is larger than the target value, the temperature of the evaporation source 3 is lowered to lower the evaporation rate of lithium. Thereby, the deposition amount of lithium can be controlled to a predetermined amount.
- the energy of ⁇ rays is not particularly limited.
- the temperature of the substrate 4 is adjusted to a temperature between the first threshold temperature and the second threshold temperature so that lithium deposited on the substrate 4 can diffuse into the substrate 4 and thermal damage to the substrate 4 is suppressed.
- a step of depositing lithium on the substrate 4 can be performed.
- the “first threshold temperature” is a lower limit temperature necessary for diffusing lithium into the substrate 4.
- the “second threshold temperature” is an upper limit temperature necessary to prevent thermal damage to the substrate 4.
- the first threshold temperature is, for example, 250 ° C., preferably 300 ° C.
- the second threshold temperature is, for example, 400 ° C., preferably 350 ° C.
- the step of controlling the deposition step includes controlling the deposition rate of lithium on the substrate 4. Specifically, it is sufficient to control only the lithium deposition rate. Therefore, the design of the feedback system is easy and the production cost can be reduced.
- a negative electrode for a lithium secondary battery was produced using the deposition amount measuring device (vacuum evaporation device) and the deposition amount measuring method described in the embodiment.
- a lithium secondary battery was produced using the negative electrode, and its characteristics were measured.
- ⁇ Production of negative electrode> A 10 ⁇ m thick silicon oxide (SiO 0.3 ) thin film was deposited on the 35 ⁇ m thick electrolytic copper foil roughened by electrolytic plating. An electrolytic copper foil provided with a silicon oxide thin film was used as a substrate, and lithium was deposited under several conditions listed in Table 1 to produce a negative electrode. The substrate was allowed to run before the deposition, and the reduction rate of the backscattering yield of the first ⁇ ray and the reduction rate of the backscattering yield of the second ⁇ ray were measured according to the method described in the embodiment. In addition, 147 Pm and 14 C were used as the nuclide for the first ⁇ ray and the nuclide for the second ⁇ ray, respectively. The deposition rate of lithium was in the range of 0.1 to 1 ⁇ m / sec in terms of film thickness.
- the amount of lithium deposited was calculated by measuring the weight per unit area of the electrolytic copper foil on which lithium was deposited.
- the maximum temperature reached by the substrate was measured by examining the discoloration of the thermolabel attached to the electrolytic copper foil.
- FIG. 2 is a schematic cross-sectional view of a lithium secondary battery manufactured using the negative electrodes of Samples 1, 3, 4, and 6.
- the lithium secondary battery includes an electrode 21 (negative electrode), a counter electrode (metal lithium positive electrode) 23 facing the electrode 21, a separator 22 interposed between the counter electrode 23 and the electrode 21 and containing an electrolyte that conducts lithium ions, Have A metal disc 24 for collecting current from the electrode 21 is provided on the surface of the electrode 21 that is not opposed to the counter electrode 23. A disc spring 25 for pressurizing the electrode 21 is disposed between the metal disk 24 and the bottom surface of the coin-type battery case 26.
- the electrode 21 and the counter electrode 23 are housed in a coin-type battery case 26 together with the separator 22 and the electrolyte, and are sealed by a sealing plate 27 having a gasket 28. Further, the battery case 26 and the sealing plate 27 are electrically connected to the electrode 21 and the counter electrode 23, respectively, and also function as positive and negative terminals.
- a lithium metal foil having a thickness of 300 ⁇ m (made by Honjo Chemical Co., Ltd.) as the counter electrode and a polyethylene microporous film (made by Asahi Kasei Co., Ltd.) having a thickness of 20 ⁇ m as the separator were used.
- a secondary battery (diameter: 20 mm, thickness 1.6 mm) was produced.
- As an electrolytic solution a solution obtained by dissolving lithium hexafluorophosphate (LiPF 6 ) at a concentration of 1 mol / L in a 1: 1 (volume ratio) mixed solvent of ethylene carbonate and diethyl carbonate. was used. The impregnation with the electrolytic solution was performed by immersing the separator and the electrode (negative electrode) in the electrolytic solution for 10 seconds.
- each lithium secondary battery is stored in a constant temperature bath at 20 ° C., charged at a constant current of 1 mA / cm 2 until the battery voltage reaches 1.5V, and then the voltage is reduced to 0.0V. It discharged with the constant current of 1 mA / cm ⁇ 2 > until it became.
- the ratio of the discharge capacity with respect to the charge capacity was determined and used as the charge / discharge efficiency.
- Table 2 shows the results of the charge / discharge cycle test.
- the reduction rate of the backscattering yield of the first ⁇ ray is equal to the reduction rate of the backscattering yield of the second ⁇ ray. That is, if the vapor deposition conditions of sample 1, 3 or 4 are adopted, the deposited lithium is reliably diffused into the active material layer. Therefore, even if only one ⁇ -ray source is used, the amount of lithium deposited can be known.
- an electrode for an electrochemical device a negative electrode for a lithium secondary battery
- a material containing lithium while appropriately controlling the amount of lithium deposited and the diffusion state of lithium Can be deposited and occluded on the substrate as an electrode, thereby reducing the initial irreversible capacity.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
リチウムと化合物を形成する層を付与した基板にリチウムを堆積させる堆積工程と、
前記堆積工程の前に、前記基板に対し、第1β線源を用いて第1β線と、前記第1β線源の核種とは異なる核種を含む第2β線源を用いて第2β線とを照射する第1のβ線照射工程と、
前記第1のβ線照射工程で照射された、前記第1β線及び前記第2β線の前記基板からの後方散乱を測定する第1の測定工程と、
前記堆積工程の後に、前記第1β線及び前記第2β線を前記基板に照射する第2のβ線照射工程と、
前記第2のβ線照射工程で照射された、前記第1β線及び前記第2β線の前記基板からの後方散乱を測定する第2の測定工程と、
前記第1の測定工程で得た結果と前記第2の測定工程で得た結果とを用いて、前記第1β線の後方散乱の減少量及び前記第2β線の後方散乱の減少量を計算する計算工程と、
前記第1β線の後方散乱の減少量及び前記第2β線の後方散乱の減少量に応じて、前記堆積工程の制御を行う制御工程と、
を含む、電気化学素子用電極の製造方法を提供する。
リチウムと化合物を形成する層を付与した基板上に堆積したリチウムの量を測定する装置であって、
前記基板に第1β線を照射する第1β線源と、
前記第1β線源の核種とは異なる核種を有し、前記基板に第2β線を照射する第2β線源と、
前記第1β線源及び前記第2β線源から照射された、前記第1β線及び前記第2β線の前記基板からの後方散乱を測定するβ線検出器と、
を備えた、堆積量測定装置を提供する。
リチウムと化合物を形成する層を付与した基板にリチウムを堆積させる堆積工程と、
前記堆積工程の前に、前記基板に対し、第1β線源を用いて第1β線と、前記第1β線源の核種と異なる核種を有する第2β線源を用いて第2β線とを照射する第1のβ線照射工程と、
前記第1のβ線照射工程で照射された、前記第1β線及び前記第2β線の前記基板からの後方散乱を測定する第1の測定工程と、
前記堆積工程の後に、前記第1β線及び前記第2β線を前記基板に照射する第2のβ線照射工程と、
前記第2のβ線照射工程で照射された、前記第1β線及び前記第2β線の前記基板からの後方散乱を測定する第2の測定工程と、
前記第1の測定工程で得た結果と前記第2の測定工程で得た結果とを用いて、前記第1β線の後方散乱の減少量及び前記第2β線の後方散乱の減少量を計算する計算工程と、
を含む、堆積量測定方法を提供する。
リチウムと化合物を形成する層を付与した基板を準備する工程と、
前記基板に堆積したリチウムが前記基板の内部に拡散でき、かつ前記基板の熱損傷を抑制するように、前記基板の温度を第1閾値温度と第2閾値温度との間の温度に調節しながら、前記基板にリチウムを堆積させる堆積工程と、
前記堆積工程の前に、前記基板に対してβ線を照射するβ線照射工程と、
前記β線照射工程で照射された、前記β線の前記基板からの後方散乱を測定する測定工程と、
前記堆積工程の後に、前記β線を前記基板に照射する第2のβ線照射工程と、
前記第2のβ線照射工程で照射された、前記β線の前記基板からの後方散乱を測定する第2の測定工程と、
前記第1の測定工程で得た結果と前記第2の測定工程で得た結果とを用いて、前記β線の後方散乱の減少量を計算する計算工程と、
前記β線の減少量に応じて前記堆積工程の制御を行う制御工程と、
を含む、電気化学素子用電極の製造方法を提供する。
図4Aに示すように、高エネルギーβ線は、層(基板)の比較的深部まで侵入し、かつ散乱される。そのため、高エネルギーβ線の後方散乱は、層の表面から深部までの情報を含む。他方、図4Bに示すように、低エネルギーβ線は、層の表面近傍で散乱される。そのため、低エネルギーβ線の後方散乱は、層の深部からあまり影響を受けず、主に表面近傍の情報を含む。
図1に、本発明の実施に使用できる真空蒸着装置の概略図を示す。真空蒸着装置100は、基板4に材料を蒸着する機能だけでなく、蒸着した材料の堆積量を測定する堆積量測定装置としての機能も有する。図1に示すように、真空蒸着装置100は、真空チャンバー1と、真空ポンプ2と、蒸発源3と、巻き出しロール5と、搬送ロール6a~6dと、キャンロール7と、巻き取りロール8と、第1β線後方散乱検出プローブ9aと、第2β線後方散乱検出プローブ9bとで構成される。以下、第1β線後方散乱検出プローブ9a及び第2β線後方散乱検出プローブ9bを単に「第1プローブ9a」及び「第2プローブ9b」と記載する。
次に、図3を用いて真空蒸着装置100の動作について説明する。図3は、制御器12が実行するべき工程を表している。なお、真空チャンバー1の内部の真空度は、リチウムの蒸着及びβ線の後方散乱収量の測定に適した真空度、例えば10-1~10-4Paに保たれる。「後方散乱収量の減少率」を正確に導くために、真空度は概ね一定に保たれるべきである。ただし、本発明に真空が不可欠というわけではなく、大気中でのリチウムの堆積にも本発明を適用できる。
次に、第1プローブ9a及び第2プローブ9bを用いて、走行している基板4に第1β線及び第2β線を照射する。第1β線及び第2β線の基板4からの後方散乱収量をそれぞれ測定する(ステップS3)。つまり、リチウムの堆積前の基板4を対象として、後方散乱収量を測定する。これにより、リチウムの堆積量がゼロのときの後方散乱収量が第1β線及び第2β線のそれぞれについて得られる。
続いて、蒸発源3に材料としてリチウム金属を入れ、抵抗加熱で温度を上昇させて蒸発させる(ステップS4)。堆積速度は、通常、1~1000nm/秒、リチウムの堆積量(薄膜に換算した厚み)は、1~10μmとなる。長尺の基板4を用いることにより、基板4を搬送する工程を実施しながら基板4にリチウムを堆積させる工程を実施できる。この方法は生産性に優れている。また、搬送工程及び堆積工程を実施しながら、後述する第2のβ線照射工程及び第2の測定工程を実施できる。
次に、第1プローブ9a及び第2プローブ9bを用いて、リチウム金属が蒸着された基板4に第1β線及び第2β線を照射する。第1β線及び第2β線の基板4からの後方散乱収量をそれぞれ測定する(ステップS5)。後方散乱収量は、単位時間(例えば1秒間)あたりの収量(count per sec)で表される。
次に、第1の測定工程で得た蒸着前の基板4についての測定結果と、第2の測定工程で得た蒸着後の基板4についての測定結果とを用いて、単位時間あたりの後方散乱収量の減少率(減少量)を第1β線及び第2β線のそれぞれについて計算する(ステップS6)。減少率の計算は、下記式に従って行うことができる。
(第2β線の後方散乱収量の減少率(%))=100×(Y0-Y1)/Y0
X0:蒸着前における第1β線の後方散乱収量
X1:蒸着後における第1β線の後方散乱収量
Y0:蒸着前における第2β線の後方散乱収量
Y1:蒸着後における第2β線の後方散乱収量
次に、第1β線の後方散乱収量の減少率と第2β線の後方散乱収量の減少率との差が所定の範囲内にあるかどうかを判断する(ステップS7)。減少率の差が所定の範囲内にある場合は、リチウムが基板4の内部に拡散しているものと判断し、現在の蒸着条件を変更せずに、そのまま蒸着を続ける。「所定の範囲」は、測定誤差を考慮した範囲である。例えば、減少率の差が±3%の範囲に収まっている場合には、リチウムが基板4に概ね拡散しているものと判断できる。
基板4がリチウムの拡散に適した温度に保たれていることを前提とすれば、1つのβ線源で堆積量をモニタしながら、基板4にリチウムを堆積させることができる。例えば、次のような予備実験を行って、基板4の内部にリチウムが確実に拡散できる温度条件(キャンロール7の冷却又は加熱条件)を見出す。具体的には、キャンロール7のいくつかの冷却又は加熱条件で基板4にリチウムを堆積させる。第1β線の後方散乱収量の減少率と、第2β線の後方散乱収量の減少率とを計算及び比較する。減少率が概ね一致しているのであれば、リチウムは基板4の内部に十分に拡散しているので、そのときの冷却又は加熱条件は適切である。
実施形態で説明した堆積量測定装置(真空蒸着装置)及び堆積量測定方法を用いて、リチウム二次電池用の負極を作製した。その負極を用いてリチウム二次電池を作製し、その特性を測定した。
電解めっきによって粗面化された厚み35μmの電解銅箔に、蒸着によって厚み10μmの酸化シリコン(SiO0.3)薄膜を堆積させた。酸化シリコン薄膜を付与した電解銅箔を基板として使用し、表1に挙げるいくつかの条件でリチウムの蒸着を行って負極を作製した。蒸着前から基板を走行させておき、実施形態で説明した方法に従って、第1β線の後方散乱収量の減少率及び第2β線の後方散乱収量の減少率を測定した。なお、第1β線の核種及び第2β線の核種として、それぞれ、147Pm及び14Cを使用した。リチウムの堆積速度は、膜厚に換算して、0.1~1μm/秒の範囲内であった。
上記方法で得られたサンプル1、3及び4の負極、並びに、リチウムを蒸着しなかった負極(サンプル6)をそれぞれ直径が12.5mmの円形に打ち抜いて、リチウム二次電池用の負極を形成した。次いで、得られた負極を用いて、それぞれ、リチウム二次電池を作製した。
続いて、得られたリチウム二次電池の充放電サイクル試験を行った。
表1に示すように、サンプル1、3及び4では、第1β線の後方散乱収量の減少率及び第2β線β線の後方散乱収量の減少率は、リチウムの堆積量にほぼ比例していた。このことは、リチウムの堆積量を正確に測定できたことを意味している。なお、表1中の「堆積量」は、リチウムが基板(正確にはシリコン薄膜)の内部に拡散せずに、基板の表面にリチウム金属の状態で堆積した場合の換算厚みで表されている。
Claims (17)
- リチウムと化合物を形成する層を付与した基板にリチウムを堆積させる堆積工程と、
前記堆積工程の前に、前記基板に対し、第1β線源を用いて第1β線と、前記第1β線源の核種とは異なる核種を含む第2β線源を用いて第2β線とを照射する第1のβ線照射工程と、
前記第1のβ線照射工程で照射された、前記第1β線及び前記第2β線の前記基板からの後方散乱を測定する第1の測定工程と、
前記堆積工程の後に、前記第1β線及び前記第2β線を前記基板に照射する第2のβ線照射工程と、
前記第2のβ線照射工程で照射された、前記第1β線及び前記第2β線の前記基板からの後方散乱を測定する第2の測定工程と、
前記第1の測定工程で得た結果と前記第2の測定工程で得た結果とを用いて、前記第1β線の後方散乱の減少量及び前記第2β線の後方散乱の減少量を計算する計算工程と、
前記第1β線の後方散乱の減少量及び前記第2β線の後方散乱の減少量に応じて、前記堆積工程の制御を行う制御工程と、
を含む、電気化学素子用電極の製造方法。 - 前記基板を搬送する搬送工程をさらに含み、
前記基板が長尺の基板である、請求項1に記載の電気化学素子用電極の製造方法。 - 前記搬送工程を実施しながら前記堆積工程を実施する、又は前記搬送工程及び前記堆積工程を間欠的に実施する、請求項2に記載の電気化学素子用電極の製造方法。
- リチウムが堆積した堆積済み部分と、リチウムが堆積していない未堆積部分とが前記長尺の基板に形成されるように、前記搬送工程を実施しながら前記堆積工程を実施し、
前記堆積済み部分を対象として、前記第2のβ線照射工程、前記第2の測定工程及び前記計算工程の各工程を実施し、前記未堆積部分へのリチウムの堆積に前記計算工程の結果がフィードバックされるように前記制御工程を実施する、請求項2に記載の電気化学素子用電極の製造方法。 - 前記搬送工程が、円筒状キャンに沿った前記基板の搬送を含み、
前記基板が前記キャンに沿った場所に、リチウムを堆積させるための領域が存在し、
前記制御工程が前記キャンの温度制御を含む、請求項2に記載の電気化学素子用電極の製造方法。 - 前記搬送工程が、加熱ロールに沿った前記基板の搬送を含み、
リチウムを堆積させるための領域を通過後に前記基板が前記加熱ロールに沿って搬送され、
前記制御工程が前記加熱ロールの温度制御を含む、請求項2に記載の電気化学素子用電極の製造方法。 - 前記堆積工程が、前記基板にリチウムが堆積するように蒸発源からリチウムを蒸発させることを含み、
前記制御工程が前記蒸発源の蒸発速度制御を含む、請求項2に記載の電気化学素子用電極の製造方法。 - 前記第1β線源が核種として147Pmを含み、
前記第2β線源が核種として14Cを含む、請求項1に記載の電気化学素子用電極の製造方法。 - リチウムと化合物を形成する層を付与した基板上に堆積したリチウムの量を測定する装置であって、
前記基板に第1β線を照射する第1β線源と、
前記第1β線源の核種とは異なる核種を有し、前記基板に第2β線を照射する第2β線源と、
前記第1β線源及び前記第2β線源から照射された、前記第1β線及び前記第2β線の前記基板からの後方散乱を測定するβ線検出器と、
を備えた、堆積量測定装置。 - 前記基板を搬送する搬送系と、
前記基板にリチウムを堆積させる蒸発源と、をさらに備えた、請求項9に記載の堆積量測定装置。 - (i)リチウムを堆積させる前の前記基板に前記第1β線及び前記第2β線を照射して前記第1β線の後方散乱及び前記第2β線の後方散乱を測定し、かつリチウムを堆積させた後の前記基板に前記第1β線及び前記第2β線を照射して前記第1β線の後方散乱及び前記第2β線の後方散乱を測定するように、前記第1β線源、前記第2β線源及び前記β線検出器を制御し、かつ(ii)リチウムの堆積の前後における、前記第1β線の後方散乱の減少量及び前記第2β線の後方散乱の減少量をそれぞれ計算する制御器をさらに備えた、請求項10に記載の堆積量測定装置。
- 前記第1β線源が核種として147Pmを含み、
前記第2β線源が核種として14Cを含む、請求項9に記載の堆積量測定装置。 - リチウムと化合物を形成する層を付与した基板にリチウムを堆積させる堆積工程と、
前記堆積工程の前に、前記基板に対し、第1β線源を用いて第1β線と、前記第1β線源の核種と異なる核種を有する第2β線源を用いて第2β線とを照射する第1のβ線照射工程と、
前記第1のβ線照射工程で照射された、前記第1β線及び前記第2β線の前記基板からの後方散乱を測定する第1の測定工程と、
前記堆積工程の後に、前記第1β線及び前記第2β線を前記基板に照射する第2のβ線照射工程と、
前記第2のβ線照射工程で照射された、前記第1β線及び前記第2β線の前記基板からの後方散乱を測定する第2の測定工程と、
前記第1の測定工程で得た結果と前記第2の測定工程で得た結果とを用いて、前記第1β線の後方散乱の減少量及び前記第2β線の後方散乱の減少量を計算する計算工程と、
を含む、堆積量測定方法。 - 前記第1β線源が核種として147Pmを含み、
前記第2β線源が核種として14Cを含む、請求項13に記載の堆積量測定方法。 - リチウムと化合物を形成する層を付与した基板を準備する工程と、
前記基板に堆積したリチウムが前記基板の内部に拡散でき、かつ前記基板の熱損傷を抑制するように、前記基板の温度を第1閾値温度と第2閾値温度との間の温度に調節しながら、前記基板にリチウムを堆積させる堆積工程と、
前記堆積工程の前に、前記基板に対してβ線を照射するβ線照射工程と、
前記β線照射工程で照射された、前記β線の前記基板からの後方散乱を測定する測定工程と、
前記堆積工程の後に、前記β線を前記基板に照射する第2のβ線照射工程と、
前記第2のβ線照射工程で照射された、前記β線の前記基板からの後方散乱を測定する第2の測定工程と、
前記第1の測定工程で得た結果と前記第2の測定工程で得た結果とを用いて、前記β線の後方散乱の減少量を計算する計算工程と、
前記β線の減少量に応じて前記堆積工程の制御を行う制御工程と、
を含む、電気化学素子用電極の製造方法。 - 前記基板が銅又は銅合金でできており、
前記第1閾値温度が250℃であり、前記第2閾値温度が400℃である、請求項15に記載の電気化学素子用電極の製造方法。 - 前記制御工程が前記基板へのリチウムの堆積速度を制御することを含む、請求項15に記載の電気化学素子用電極の製造方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2010800322950A CN102473904A (zh) | 2009-07-24 | 2010-07-02 | 沉积量测定装置、沉积量测定方法及电化学元件用电极的制造方法 |
US13/384,928 US9028922B2 (en) | 2009-07-24 | 2010-07-02 | Deposition quantity measuring apparatus, deposition quantity measuring method, and method for manufacturing electrode for electrochemical element |
JP2010542423A JP4794694B2 (ja) | 2009-07-24 | 2010-07-02 | 堆積量測定装置、堆積量測定方法及び電気化学素子用電極の製造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009-172708 | 2009-07-24 | ||
JP2009172708 | 2009-07-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011010430A1 true WO2011010430A1 (ja) | 2011-01-27 |
Family
ID=43498911
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/004365 WO2011010430A1 (ja) | 2009-07-24 | 2010-07-02 | 堆積量測定装置、堆積量測定方法及び電気化学素子用電極の製造方法 |
Country Status (4)
Country | Link |
---|---|
US (1) | US9028922B2 (ja) |
JP (1) | JP4794694B2 (ja) |
CN (1) | CN102473904A (ja) |
WO (1) | WO2011010430A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023017689A1 (ja) * | 2021-08-11 | 2023-02-16 | 信越化学工業株式会社 | 負極 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9689820B2 (en) | 2011-10-25 | 2017-06-27 | Purdue Research Foundation | Thermography for battery component quality assurance |
JP6868962B2 (ja) * | 2016-03-11 | 2021-05-12 | 株式会社Screenホールディングス | 膜・電極層接合体の製造装置および製造方法 |
EP4095939A1 (de) * | 2021-05-28 | 2022-11-30 | Siemens Aktiengesellschaft | Verfahren zum herstellen einer batteriezelle |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000353515A (ja) * | 1999-06-11 | 2000-12-19 | Toyota Central Res & Dev Lab Inc | 電池用シート電極の製造方法 |
JP2002025541A (ja) * | 2000-07-07 | 2002-01-25 | Matsushita Electric Ind Co Ltd | 電池用電極板の製造方法および製造装置 |
JP2002231221A (ja) * | 2001-02-01 | 2002-08-16 | Mitsubishi Heavy Ind Ltd | リチウム二次電池用電極又はセパレータ及びこれらの製造方法並びにこれらを用いたリチウム二次電池 |
WO2009142019A1 (ja) * | 2008-05-21 | 2009-11-26 | パナソニック株式会社 | 薄膜の製造方法 |
JP2010140793A (ja) * | 2008-12-12 | 2010-06-24 | Panasonic Corp | 非水電解質二次電池用負極の製造方法、非水電解質二次電池用負極、および非水電解質二次電池 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3405267A (en) * | 1964-06-17 | 1968-10-08 | Industrial Nucleonics Corp | Inner layer displacement measuring method and apparatus |
US3665199A (en) * | 1969-11-10 | 1972-05-23 | Ohmart Corp | Beta-ray thickness gauge using a two energy level beta-ray source |
JPS544828A (en) | 1977-06-14 | 1979-01-13 | Nippon Electro Plating | Method of adjusting plating thickness in automatic continuous plating and measuring device therefor |
US4293767A (en) * | 1979-08-24 | 1981-10-06 | Helmut Fischer | Apparatus for measuring the thickness of thin layers |
JPH01173810A (ja) | 1987-12-28 | 1989-07-10 | Sumitomo Metal Ind Ltd | 塗装膜厚測定方法 |
JPH08219748A (ja) | 1995-02-20 | 1996-08-30 | Sumitomo Metal Ind Ltd | β線膜厚計による塗膜厚測定方法 |
KR100324624B1 (ko) | 2000-02-26 | 2002-02-27 | 박호군 | 다공성 금속, 금속산화물 또는 탄소 박막이 피복된금속산화물전극 및 그 제조방법, 이를 이용한 리튬 이차전지 |
JP2004303597A (ja) | 2003-03-31 | 2004-10-28 | Sanyo Electric Co Ltd | リチウム二次電池およびその製造方法 |
TWI249868B (en) | 2003-09-09 | 2006-02-21 | Sony Corp | Anode and battery |
JP2005085632A (ja) | 2003-09-09 | 2005-03-31 | Sony Corp | 電池 |
US7736802B1 (en) * | 2004-11-12 | 2010-06-15 | Greatbatch Ltd. | Electrochemical cell current collector comprising solid area for coated film measurements |
JP5092280B2 (ja) | 2006-05-24 | 2012-12-05 | ソニー株式会社 | 二次電池用電極及びその製造方法、並びに二次電池 |
US8274056B2 (en) * | 2010-01-07 | 2012-09-25 | Battelle Energy Alliance, Llc | Method, apparatus and system for low-energy beta particle detection |
-
2010
- 2010-07-02 US US13/384,928 patent/US9028922B2/en not_active Expired - Fee Related
- 2010-07-02 JP JP2010542423A patent/JP4794694B2/ja not_active Expired - Fee Related
- 2010-07-02 WO PCT/JP2010/004365 patent/WO2011010430A1/ja active Application Filing
- 2010-07-02 CN CN2010800322950A patent/CN102473904A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000353515A (ja) * | 1999-06-11 | 2000-12-19 | Toyota Central Res & Dev Lab Inc | 電池用シート電極の製造方法 |
JP2002025541A (ja) * | 2000-07-07 | 2002-01-25 | Matsushita Electric Ind Co Ltd | 電池用電極板の製造方法および製造装置 |
JP2002231221A (ja) * | 2001-02-01 | 2002-08-16 | Mitsubishi Heavy Ind Ltd | リチウム二次電池用電極又はセパレータ及びこれらの製造方法並びにこれらを用いたリチウム二次電池 |
WO2009142019A1 (ja) * | 2008-05-21 | 2009-11-26 | パナソニック株式会社 | 薄膜の製造方法 |
JP2010140793A (ja) * | 2008-12-12 | 2010-06-24 | Panasonic Corp | 非水電解質二次電池用負極の製造方法、非水電解質二次電池用負極、および非水電解質二次電池 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023017689A1 (ja) * | 2021-08-11 | 2023-02-16 | 信越化学工業株式会社 | 負極 |
Also Published As
Publication number | Publication date |
---|---|
US20120121794A1 (en) | 2012-05-17 |
JP4794694B2 (ja) | 2011-10-19 |
US9028922B2 (en) | 2015-05-12 |
JPWO2011010430A1 (ja) | 2012-12-27 |
CN102473904A (zh) | 2012-05-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Ma et al. | Toward practical high‐areal‐capacity aqueous zinc‐metal batteries: quantifying hydrogen evolution and a solid‐ion conductor for stable zinc anodes | |
Kolesnikov et al. | Galvanic corrosion of lithium‐powder‐based electrodes | |
Hou et al. | Unraveling the rate‐dependent stability of metal anodes and its implication in designing cycling protocol | |
JP4802570B2 (ja) | リチウムイオン二次電池用負極、その製造方法、およびそれを用いたリチウムイオン二次電池 | |
JP4794694B2 (ja) | 堆積量測定装置、堆積量測定方法及び電気化学素子用電極の製造方法 | |
Pereira-Nabais et al. | Effect of lithiation potential and cycling on chemical and morphological evolution of Si thin film electrode studied by ToF-SIMS | |
KR20080069664A (ko) | 비수전해질 이차전지용 전극과 그 제조 방법 및 비수전해질 이차전지용 전극을 갖춘 비수 전해질 이차전지 | |
Tsuchiya et al. | In Situ Direct Lithium Distribution Analysis Around Interfaces in an All‐Solid‐State Rechargeable Lithium Battery by Combined Ion‐Beam Method | |
BR112013021247B1 (pt) | Material de eletrodo, capacitor eletrolítico sólido, folha de catodo para uso em um capacitor eletrolítico sólido, coletor de corrente para um eletrodo, eletrodos positivo e negativo para uma bateria secundária eletrolítica não aquosa e para um capacitor híbrido eletrolítico não aquoso, bateria secundária eletrolítica não aquosa, eletrodo para um capacitor de camada elétrica dupla eletrolítica não aquosa, capacitor de camada elétrica dupla eletrolítica não aquosa, e, capacitor híbrido eletrolítico não aquoso | |
US10837098B2 (en) | Method and coating arrangement | |
JP6515695B2 (ja) | リチウムイオン二次電池、電池パック、リチウムイオン二次電池の劣化検出装置及び劣化検出方法 | |
Wang et al. | Profiling lithium distribution in Sn anode for lithium-ion batteries with neutrons | |
Nagpure et al. | Discovery of lithium in copper current collectors used in batteries | |
JP2007122992A (ja) | リチウム二次電池用負極およびリチウム二次電池の製造方法 | |
CN112909232A (zh) | 一种氟化钠浸渍包覆钒掺杂多孔结构焦磷酸铁钠正极材料及其制备方法 | |
JP5181585B2 (ja) | リチウム二次電池用負極の製造法 | |
Hagemeister et al. | Lean Cell Finalization in Lithium‐Ion Battery Production: Determining the Required Electrolyte Wetting Degree to Begin the Formation | |
JP2013026444A (ja) | 非水電解質電気化学素子用電極の製造方法およびその非水電解質電気化学素子用電極を備えた非水電解質電気化学素子 | |
JP3979800B2 (ja) | リチウム二次電池用電極の形成装置および形成方法 | |
Price et al. | Search for energetic-charged-particle emission from deuterated Ti and Pd foils | |
Auer et al. | Optimized Design Principles for Silicon‐Coated Nanostructured Electrode Materials and their Application in High‐Capacity Lithium‐Ion Batteries | |
JP2010140793A (ja) | 非水電解質二次電池用負極の製造方法、非水電解質二次電池用負極、および非水電解質二次電池 | |
JP2007220450A (ja) | リチウム二次電池用負極板、およびそれを用いたリチウム二次電池 | |
JP2007207663A (ja) | リチウムイオン二次電池用負極の製造方法およびその方法を用いて得られた負極を含むリチウムイオン二次電池 | |
JP2017004605A (ja) | リチウム硫黄二次電池及びセパレータの製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080032295.0 Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 2010542423 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10802052 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13384928 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 10802052 Country of ref document: EP Kind code of ref document: A1 |