CN110137490A - A kind of method of phosphate anion doping mangaic acid cobalt lithium anode material - Google Patents

A kind of method of phosphate anion doping mangaic acid cobalt lithium anode material Download PDF

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Publication number
CN110137490A
CN110137490A CN201910476901.0A CN201910476901A CN110137490A CN 110137490 A CN110137490 A CN 110137490A CN 201910476901 A CN201910476901 A CN 201910476901A CN 110137490 A CN110137490 A CN 110137490A
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phosphate anion
cobalt lithium
anode material
acid cobalt
mangaic acid
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杨志远
王聪
张天赐
陈中华
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Hubei Lithium Nuo Amperex Technology Ltd
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Hubei Lithium Nuo Amperex Technology Ltd
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/028—Positive 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

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  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention relates to technical field of lithium batteries more particularly to a kind of methods of phosphate anion doping mangaic acid cobalt lithium anode material.The method of phosphate anion doping mangaic acid cobalt lithium anode material of the invention, which is characterized in that comprising steps of (1) is by CoCl2·6H2O、MnCl2·4H2O, urea, ascorbic acid and polyvinylpyrrolidone dissolution obtain mixed solution, CoCl in deionized water2·6H2O and MnCl2·4H2The molar ratio of O is 1:1；(2) mixed solution drops to room temperature in 150~170 DEG C of 6~12h of reaction, successively through centrifugation, wash, be dried to obtain solids；(3) by solids and NH4H2PO4And LiOHH2O mixing, LiOHH2O、CoCl2·6H2O and MnCl2·4H2The molar ratio of O is 1.01~1.03:1:1, and calcining obtains phosphate anion doping mangaic acid cobalt lithium anode material in oxygen.The method of phosphate anion doping mangaic acid cobalt lithium anode material of the invention can be improved the reversible discharge capacity and capacity retention ratio of battery.

Description

A kind of method of phosphate anion doping mangaic acid cobalt lithium anode material
Technical field
The present invention relates to technical field of lithium batteries more particularly to a kind of phosphate anion to adulterate mangaic acid cobalt lithium anode material Method.
Background technique
In recent years, high pressure Spinel positive electrode is because it is with high-energy density and high rate capability and with three-dimensional lithium Ion transmission path, and the extensive concern by people.High-voltage positive electrode material such as LiCoMnO4、LiNi0.5Mn1.5O4With LiCoPO4, wherein LiCoMnO4Show higher potential (5V, Li+/Li)。
Since the oxygen loss in spinel crystal lattice can generate Li when synthesizing lithium manganese base spinelle at high temperature2MnO3It is heavy It forms sediment, Li2MnO3It is coexisted with oxygen deprivation spinelle.Therefore LiCoMnO4Capacity be extremely difficult to 75%, and capacity attenuation is very fast.
Summary of the invention
In order to solve the above problem, the object of the present invention is to provide a kind of phosphate anion doping mangaic acid cobalt lithium anode materials Method improves the reversible discharge capacity and capacity retention ratio of battery.
To achieve the above object, the method for the phosphate anion doping mangaic acid cobalt lithium anode material designed by the present invention, It is characterized in that, comprising steps of
(1) by CoCl2·6H2O、MnCl2·4H2O, urea, ascorbic acid and polyvinylpyrrolidone are dissolved in deionization Mixed solution, CoCl are obtained in water2·6H2O and MnCl2·4H2The molar ratio of O is 1:1；
(2) mixed solution drops to room temperature in 150~170 DEG C of 6~12h of reaction, successively through centrifugation, wash, be dried to obtain it is solid Body object；
(3) by solids and NH4H2PO4And LiOHH2O mixing, LiOHH2O、CoCl2·6H2O and MnCl2·4H2O Molar ratio be 1.01~1.03:1:1, in oxygen calcining obtain phosphate anion doping mangaic acid cobalt lithium (LiCoMnO4) anode Material.
Preferably, in the step (1), CoCl2·6H2O、MnCl2·4H2O, urea, ascorbic acid and poly- second The molar ratio of alkene pyrrolidone is 1:1:0.02~0.04:0.012~0.016:0.03 × 10-3~0.07 × 10-3。
Preferably, the NH4H2PO4、LiOH·H2O、CoCl2·6H2O、MnCl2·4H2The molar ratio of O is 0.03~0.07:1.01~1.03:1:1.
Preferably, the calcination temperature is 800~850 DEG C, and calcination time is 20~24 hours.
A kind of button half-cell, including electrolyte, anode electrode piece and negative electricity pole piece, which is characterized in that the anode Electrode slice includes collector and the anode sizing agent coated in collection liquid surface, the anode sizing agent in mass ratio, including 80~ 90% phosphate anion adulterates mangaic acid cobalt lithium anode material, 5~10% acetylene blacks and 5~10% Kynoar.
With it is traditional using mangaic acid cobalt lithium compared with the button half-cell of positive electrode, the present invention using phosphate anion adulterate Mangaic acid cobalt lithium (LiCoMnO4) positive electrode, phosphate anion doping mangaic acid cobalt lithium (LiCoMnO4) positive electrode, PO4 3-Doping takes For mangaic acid cobalt lithium (LiCoMnO4) in O2-, hinder Li2MnO3Generation, improve mangaic acid cobalt lithium (LiCoMnO4) structure it is steady It is qualitative, and then improve the reversible discharge capacity and capacity retention ratio of button half-cell.
Preferably, the chemical formula of the phosphate anion doping mangaic acid cobalt lithium anode material is LiCoMn (PO4)xO4-x, X is 0.03~0.07.
Preferably, the electrolyte includes the mixing of ethylene carbonate and methyl ethyl carbonate that mass ratio is 3:7 The LiPF of solvent, 1mol/L6Lithium salts and 0.5~1.5wt% LiBODFP additive.
Detailed description of the invention
Fig. 1 is the cycle performance that embodiment 4~7 is made that button half-cell recycles 50 circles under room temperature 1C multiplying power；
Fig. 2 is the capacity retention ratio that button half-cell is made and recycles 50 circles under room temperature 1C multiplying power of embodiment 4~7.
Specific embodiment
For a better understanding of the invention, invention is described in detail below with reference to drawings and concrete examples.Below Mangaic acid cobalt lithium uses chemical formula LiCoMnO4It indicates.
To solve existing LiCoMnO4Positive electrode has that capacity is small and capacity retention ratio is low, and the present invention provides A kind of phosphate anion doping LiCoMnO4The method of positive electrode adulterates PO by situ4 3-Obtain LiCoMn (PO4)xO4-x Positive electrode, PO4 3-Doped and substituted LiCoMnO4In O2-, hinder Li2MnO3Generation, improve LiCoMnO4Stable structure Property, and then improve reversible discharge capacity and capacity retention ratio.Below by by specific embodiment come to phosphate radical of the invention Ion doping LiCoMnO4The preferred embodiment of the method for positive electrode is described in detail.
Embodiment 1
Phosphate anion adulterates LiCoMnO4The method of positive electrode, comprising steps of
(1) by 1mol CoCl2·6H2O、1mol MnCl2·4H2O, 0.02mol urea, 0.012mol ascorbic acid and 0.03mmol polyvinylpyrrolidone is dissolved in 60mL deionized water and obtains mixed solution；
(2) mixed solution drops to room temperature in 150 DEG C of reaction 12h, successively through centrifugation, wash, be dried to obtain solids；
(3) by solids and 0.03mol NH4H2PO4With 1.01mol LiOHH2O mixing, 800 DEG C of calcinings in oxygen Obtain within 24 hours phosphate anion doping LiCoMnO4Positive electrode LiCoMn (PO4)0.03O3.97。
Embodiment 2
Phosphate anion adulterates LiCoMnO4The method of positive electrode, comprising steps of
(1) by 1mol CoCl2·6H2O、1mol MnCl2·4H2O, 0.04mol urea, 0.016mol ascorbic acid and 0.07mmol polyvinylpyrrolidone is dissolved in 60mL deionized water and obtains mixed solution；
(2) mixed solution drops to room temperature in 170 DEG C of reaction 6h, successively through centrifugation, wash, be dried to obtain solids；
(3) by solids and 0.05mol NH4H2PO4With 1.02mol LiOHH2O mixing, 830 DEG C of calcinings in oxygen Obtain within 22 hours phosphate anion doping LiCoMnO4Positive electrode LiCoMn (PO4)0.05O3.95。
Embodiment 3
Phosphate anion adulterates LiCoMnO4The method of positive electrode, comprising steps of
(1) by 1mol CoCl2·6H2O、1mol MnCl2·4H2O, 0.03mol urea, 0.015mol ascorbic acid and 0.05mmol polyvinylpyrrolidone is dissolved in 60mL deionized water and obtains mixed solution；
(2) mixed solution drops to room temperature in 160 DEG C of reaction 10h, successively through centrifugation, wash, be dried to obtain solids；
(3) by solids and 0.07mol NH4H2PO4With 1.02mol LiOHH2O mixing, 830 DEG C of calcinings in oxygen Obtain within 22 hours phosphate anion doping LiCoMnO4Positive electrode LiCoMn (PO4)0.07O3.93。
Embodiment 4
A kind of button half-cell, including electrolyte, anode electrode piece and negative electricity pole piece, electrolyte are that mass ratio is 3:7 Ethylene carbonate (EC) and methyl ethyl carbonate (EMC) mixed solvent, 1mol/L (contains 1mol's in one liter of electrolyte LiPF6)LiPF6Lithium salts；Anode electrode piece includes aluminium foil and the anode sizing agent layer coated in aluminium foil surface, and anode sizing agent presses matter Amount includes 85%LiCoMnO than being4Positive electrode, 5% acetylene black and 10% binder Kynoar (PVDF)；Negative electricity Pole piece is lithium metal.
Embodiment 5
A kind of button half-cell, including electrolyte, anode electrode piece and negative electricity pole piece, electrolyte are that mass ratio is 3:7 Ethylene carbonate (EC) and methyl ethyl carbonate (EMC) mixed solvent, 1mol/L (contains 1mol's in one liter of electrolyte LiPF6)LiPF6Lithium salts；Anode electrode piece includes aluminium foil and the anode sizing agent layer coated in aluminium foil surface, and anode sizing agent presses matter Amount includes 85% phosphate anion doping LiCoMnO than being4Positive electrode, 5% acetylene black and 10% binder polyvinylidene fluoride Alkene (PVDF)；Negative electricity pole piece is lithium metal.
Phosphate anion adulterates LiCoMnO4Positive electrode is the LiCoMn (PO that embodiment 1 obtains4)0.03O3.97Material.
Embodiment 6
A kind of button half-cell, including electrolyte, anode electrode piece and negative electricity pole piece, electrolyte are that mass ratio is 3:7 Ethylene carbonate (EC) and methyl ethyl carbonate (EMC) mixed solvent, 1mol/L (contains 1mol's in one liter of electrolyte LiPF6)LiPF6Lithium salts；Anode electrode piece includes aluminium foil and the anode sizing agent layer coated in aluminium foil surface, and anode sizing agent presses matter Amount includes 80% phosphate anion doping LiCoMnO than being4Positive electrode, 10% acetylene black and 10% binder polyvinylidene fluoride Alkene (PVDF)；Negative electricity pole piece is lithium metal.
Phosphate anion adulterates LiCoMnO4Positive electrode is the LiCoMn (PO that embodiment 2 obtains4)0.05O3.95Material.
Embodiment 7
A kind of button half-cell, including electrolyte, anode electrode piece and negative electricity pole piece, electrolyte are that mass ratio is 3:7 Ethylene carbonate (EC) and methyl ethyl carbonate (EMC) mixed solvent, 1mol/L (contains 1mol's in one liter of electrolyte LiPF6)LiPF6Lithium salts；Anode electrode piece includes aluminium foil and the anode sizing agent layer coated in aluminium foil surface, and anode sizing agent presses matter Amount includes 90% phosphate anion doping LiCoMnO than being4Positive electrode, 5% acetylene black and 5% binder Kynoar (PVDF)；Negative electricity pole piece is lithium metal.
Phosphate anion adulterates LiCoMnO4Positive electrode is the LiCoMn (PO that embodiment 3 obtains4)0.07O3.93Material.
Embodiment 8
A kind of button half-cell, including electrolyte, anode electrode piece and negative electricity pole piece, electrolyte are that mass ratio is 3:7 Ethylene carbonate (EC) and methyl ethyl carbonate (EMC) mixed solvent, 1mol/L (contains 1mol's in one liter of electrolyte LiPF6)LiPF6Lithium salts and 0.5wt% (in every hectogram electrolyte contain 0.5 gram of LiBODFP) LiBODFP additive；Anode Electrode slice includes aluminium foil and the anode sizing agent layer coated in aluminium foil surface, anode sizing agent be in mass ratio include 85% phosphate radical from Son doping LiCoMnO4Positive electrode, 5% acetylene black and 10% binder Kynoar (PVDF)；Negative electricity pole piece is lithium Metal.
Phosphate anion adulterates LiCoMnO4Positive electrode is the LiCoMn (PO that embodiment 2 obtains4)0.05O3.95Material.
Embodiment 9
A kind of button half-cell, including electrolyte, anode electrode piece and negative electricity pole piece, electrolyte are that mass ratio is 3:7 Ethylene carbonate (EC) and methyl ethyl carbonate (EMC) mixed solvent, 1mol/L (contains 1mol's in one liter of electrolyte LiPF6)LiPF6Lithium salts and 1.0wt% (in every hectogram electrolyte contain 1.0 grams of LiBODFP) LiBODFP additive；Anode Electrode slice includes aluminium foil and the anode sizing agent layer coated in aluminium foil surface, anode sizing agent be in mass ratio include 85% phosphate radical from Son doping LiCoMnO4Positive electrode, 5% acetylene black and 10% binder Kynoar (PVDF)；Negative electricity pole piece is lithium Metal.
Phosphate anion adulterates LiCoMnO4Positive electrode is the LiCoMn (PO that embodiment 2 obtains4)0.05O3.95Material.
Embodiment 10
A kind of button half-cell, including electrolyte, anode electrode piece and negative electricity pole piece, electrolyte are that mass ratio is 3:7 Ethylene carbonate (EC) and methyl ethyl carbonate (EMC) mixed solvent, 1mol/L (contains 1mol's in one liter of electrolyte LiPF6)LiPF6Lithium salts and 1.5wt% (in every hectogram electrolyte contain 1.5 grams of LiBODFP) LiBODFP additive；Anode Electrode slice includes aluminium foil and the anode sizing agent layer coated in aluminium foil surface, anode sizing agent be in mass ratio include 85% phosphate radical from Son doping LiCoMnO4Positive electrode, 5% acetylene black and 10% binder Kynoar (PVDF)；Negative electricity pole piece is lithium Metal.
Phosphate anion adulterates LiCoMnO4Positive electrode is the LiCoMn (PO that embodiment 2 obtains4)0.05O3.95Material.
Fig. 1 is the cycle performance that embodiment 4~7 is made that button half-cell recycles 50 circles under room temperature 1C multiplying power；Fig. 2 is real Apply the capacity retention ratio that button half-cell is made and recycles 50 circles under room temperature 1C multiplying power of example 4~7；It can from Fig. 1 and Fig. 2 Out, PO4 3-The LiCoMnO of doping4Than undoped LiCoMnO4Cyclical stability and capacity retention ratio are more preferable.
The coulombic efficiency and capacity retention ratio that button half-cell recycles 50 circles under room temperature 1C multiplying power is made in embodiment 4~10 As shown in Table 1 and Table 2.
Table 1
Embodiment Coulombic efficiency %
Embodiment 6 98.7
Embodiment 8 99.1
Embodiment 9 99.5
Embodiment 10 99.2
Table 2
Embodiment Capacity retention ratio %
Embodiment 6 93.1
Embodiment 8 94.3
Embodiment 9 95.6
Embodiment 10 94.1
As can be seen from Table 1 and Table 2, LiBODFP additive is added in the electrolytic solution, can change electrolyte and electrode Interfacial structure and ingredient form form compact and stable SEI film, so as to improve lithium ion battery coulombic efficiency and capacity retention ratio.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (7)

1. a kind of method of phosphate anion doping mangaic acid cobalt lithium anode material, which is characterized in that comprising steps of
(1) by CoCl2·6H2O、MnCl2·4H2O, urea, ascorbic acid and polyvinylpyrrolidone dissolve in deionized water Obtain mixed solution, CoCl2·6H2O and MnCl2·4H2The molar ratio of O is 1:1；
(2) mixed solution is down to room temperature in 150~170 DEG C of 6~12h of reaction, successively through centrifugation, wash, be dried to obtain solid Object；
(3) by solids and NH4H2PO4And LiOHH2O mixing, controls LiOHH2O、CoCl2·6H2O and MnCl2·4H2O Molar ratio be 1.01~1.03:1:1, in oxygen calcining obtain phosphate anion doping mangaic acid cobalt lithium anode material.
2. the method for phosphate anion according to claim 1 doping mangaic acid cobalt lithium anode material, in the step (1), CoCl2·6H2O、MnCl2·4H2O, the molar ratio of urea, ascorbic acid and polyvinylpyrrolidone is 1:1:0.02~0.04: 0.012~0.016:0.03 × 10-3~0.07 × 10-3。
3. the method for phosphate anion doping mangaic acid cobalt lithium anode material according to claim 1, the NH4H2PO4、 LiOH·H2O、CoCl2·6H2O、MnCl2·4H2The molar ratio of O is 0.03~0.07:1.01~1.03:1:1.
4. the method for phosphate anion doping mangaic acid cobalt lithium anode material according to claim 1, the calcination temperature are 800~850 DEG C, calcination time is 20~24 hours.
5. a kind of button half-cell, including electrolyte, anode electrode piece and negative electricity pole piece, which is characterized in that the anode electricity Pole piece includes collector and the anode sizing agent coated in collection liquid surface, the anode sizing agent in mass ratio, including 80~90% Phosphate anion adulterates mangaic acid cobalt lithium anode material, 5~10% acetylene blacks and 5~10% Kynoar.
6. button half-cell according to claim 5, which is characterized in that the phosphate anion adulterates mangaic acid cobalt lithium anode material The chemical formula of material is LiCoMn (PO4)xO4-x, X is 0.03~0.07.
7. button half-cell according to claim 5, which is characterized in that the electrolyte includes the carbonic acid that mass ratio is 3:7 The LiPF of the mixed solvent of vinyl acetate and methyl ethyl carbonate, 1mol/L6Lithium salts and 0.5~1.5wt% LiBODFP addition Agent.
CN201910476901.0A 2019-06-03 2019-06-03 A kind of method of phosphate anion doping mangaic acid cobalt lithium anode material Pending CN110137490A (en)

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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN102324515A (en) * 2011-09-20 2012-01-18 湖南升华科技有限公司 The lithium manganate having spinel structure preparation method reaches by its LiMn2O4 that makes and battery
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Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN102324515A (en) * 2011-09-20 2012-01-18 湖南升华科技有限公司 The lithium manganate having spinel structure preparation method reaches by its LiMn2O4 that makes and battery
CN103794776A (en) * 2014-02-13 2014-05-14 湖南美特新材料科技有限公司 High-voltage high-compaction composite positive electrode material of lithium ion battery and preparation method

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Title
ANNA WINDMÜLLER等: "Enhancing the performance of high-voltage LiCoMnO4 spinel electrodes by fluorination", 《JOURNAL OF POWER SOURCES》 *
LONG CHEN等: "Achieving High Energy Density through Increasing the Output Voltage: A Highly Reversible 5.3 V Battery", 《CHEM》 *
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