AU2021103929A4 - Preparation method and application of Ni-containing CuS/C composite material - Google Patents
Preparation method and application of Ni-containing CuS/C composite material Download PDFInfo
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- AU2021103929A4 AU2021103929A4 AU2021103929A AU2021103929A AU2021103929A4 AU 2021103929 A4 AU2021103929 A4 AU 2021103929A4 AU 2021103929 A AU2021103929 A AU 2021103929A AU 2021103929 A AU2021103929 A AU 2021103929A AU 2021103929 A4 AU2021103929 A4 AU 2021103929A4
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- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 68
- 239000002243 precursor Substances 0.000 claims abstract description 207
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000011259 mixed solution Substances 0.000 claims abstract description 79
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 67
- 239000000243 solution Substances 0.000 claims abstract description 61
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910000570 Cupronickel Inorganic materials 0.000 claims abstract description 51
- 239000011593 sulfur Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 15
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000007774 positive electrode material Substances 0.000 claims abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 78
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 73
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 53
- 238000000227 grinding Methods 0.000 claims description 52
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 50
- 239000000463 material Substances 0.000 claims description 50
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 31
- 238000003763 carbonization Methods 0.000 claims description 29
- 230000004913 activation Effects 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 26
- 229910052786 argon Inorganic materials 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000008213 purified water Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 19
- 238000003760 magnetic stirring Methods 0.000 claims description 18
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 239000013110 organic ligand Substances 0.000 claims description 12
- 150000001879 copper Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 23
- 229910052799 carbon Inorganic materials 0.000 abstract description 22
- 229920001021 polysulfide Polymers 0.000 abstract description 11
- 239000005077 polysulfide Substances 0.000 abstract description 11
- 150000008117 polysulfides Polymers 0.000 abstract description 11
- 238000007599 discharging Methods 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 4
- 238000010000 carbonizing Methods 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 66
- 238000012512 characterization method Methods 0.000 description 18
- 239000012071 phase Substances 0.000 description 15
- 239000010949 copper Substances 0.000 description 13
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 13
- 125000004122 cyclic group Chemical group 0.000 description 12
- 230000002441 reversible effect Effects 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 11
- 238000011056 performance test Methods 0.000 description 11
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000010998 test method Methods 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 229910052976 metal sulfide Inorganic materials 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical class [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910001453 nickel ion Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 239000005749 Copper compound Substances 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 150000004684 trihydrates Chemical class 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910018091 Li 2 S Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The present invention relates to a preparation method and application of a
Ni-containing CuS/C composite material. The preparation method comprises
following steps of: preparing a copper-nickel ion mixed solution, preparing a
precursor reaction solution, preparing a precursor, removing impurities, activating the
precursor, and vulcanizing and carbonizing the precursor, and the Ni-containing
CuS/C composite material provided by the present invention is applied to a positive
electrode material of a lithium-sulfur battery. The unique porous carbon frame
structure of the Ni-containing CuS/C composite material provided in the present
invention is beneficial to improve discharging capability of a battery, polysulfide ion
shuttling can be effectively inhibited by bimetallic ion sulfur fixation, and the volume
expansion problem is inhibited by bimetallic ion synergism. The preparation method
disclosed by the present invention is simple in process and environment-friendly, does
not need high temperature and high pressure, can directly use pure sulfur as a sulfur
source, is not liable to generate pollution gases and byproducts, and can be made in a
common laboratory without high temperature and high pressure conditions.
2/2
CuS PDF#06-0468
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Figure 3
Figure 4
Description
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CuS PDF#06-0468
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Figure 4
Preparation method and application of Ni-containing CuS/C composite material
Technical Field
The present invention relates to a method, by using nickel-doped copper-based metal
organic frame material, for preparing metal sulfide which is then applied to the
lithium-sulfur battery energy storage system, in particular to a preparation method and
application of Ni-containing CuS/C composite material.
Background Technology
With the development of science, technology and economy, the requirements of
electronic devices for mobile power are increasing. Lithium-ion energy storage
system and batteries have received great attention and achieved significant
development due to their high specific energy density, long life cycle and good safety
performance. Among them, the lithium-sulfur battery is a kind of lithium battery with
a sulfur element as the positive electrode and lithium metal as the negative electrode.
The lithium-sulfur battery is considered to be one of the most promising next
generation energy storage batteries because of being of low cost, high theoretical
specific capacity (1675mA/hg) and energy density (2600Wh/kg). However, the
capacity attenuation of lithium-sulfur batteries caused by the polysulfide shuttling,
and the poor discharging performance caused by insulation of elemental sulfur and
Li 2 S, have seriously hindered development and application of lithium-sulfur batteries.
As a result, currently, researches on lithium-sulfur batteries are mainly about
combining sulfur with carbon materials, or combining sulfur with organics, thereby
solving the problem of non-conductivity and volume expansion of sulfur. Compared
with the traditional lithium-sulfur battery materials, metal sulfide/carbon composites
have characteristics of higher theoretical capacity, good electrical conductivity and
chemical sulfur fixation. And addition of materials with good conductivity is
beneficial to improve the discharging performance of the battery, and the strong
adsorption capacity of polysulfide ions can inhibit polysulfide shuttling.
Copper sulfide/carbon composite is a promising cathode material for lithium-ion
batteries due to its low cost, high theoretical capacity and various synthesis methods.
At present, commonly used methods for synthesis of metal sulfide/carbon composites
are hydrothermal method and solvothermal method. However, existing methods and
metal sulfide/carbon composites have following defects:
I. Existing metal sulfide/carbon composites are formed under a reaction of high
temperature and high pressure, and morphology and size thereof are not uniform,
crystallinity thereof is not high, and composite bonding thereof is not tight enough.
II. Carbon framework structure of existing copper sulfide/carbon composites are not
sufficient to satisfy volume expansion of the metal sulfide in the electrochemical
reaction, thereby leading to electrode powdering and easy separation of the metal
sulfide and carbon, and results in reducing of electrochemical properties of the copper
sulfide/carbon composites.
III. The sulfur source used in the hydrothermal method and the solvothermal method
is generally organic sulfur, which is liable to produce polluting gases and by-products.
Moreover, under high temperature and high pressure conditions, high requirements
are on the equipment and the process is complicated.
IV. In a traditional process, mixing of the metallic phase and the conductive phase is
done by hydrothermal process, solid phase blending and other methods. There is no
chemical bond between the metal and carbon, which leads to an uneven metal
distribution, easy agglomeration and poor physical and chemical homogeneity of the
material, thereby directly leading to a poor uniformity of the battery.
V. Although the existing copper sulfide/carbon composite materials have solved the
shuttling problem of polysulfide ions to a certain extent, but not as expected,
indicating that the use of copper sulfide/carbon composite materials to suppress the
shuttling problem of polysulfide ions still remains to be explored.
Summary of Invention
In order to solve the above problems, the present invention prepares a Ni-containing
CuS/C composite material by means of vulcanizing and carbonizing a self-made nickel-doped copper based organic frame material. The in-situ prepared carbon composite does not only make morphology of the Ni-containing CuS/C composite material more uniform, and the Ni-containing CuS/C composite material tighter, but also can improve the crystallinity thereof; a powdered sulfur vulcanization method is not only simple, low cost, but also produces less polluting gases and by-products; the
Ni-containing CuS/C composite material provided by the present invention can
effectively utilize bimetallic elements to absorb polysulfide ions, effectively reduce
polysulfide shuttling, volume expansion, capacity attenuation and uneven morphology
problems, and can improve the conductivity of the Ni-containing CuS/C composite
material and improve energy storage performance of the lithium-sulfur battery
comprehensively.
A preparation method of the Ni-containing CuS/C composite material according to the
present invention comprises following steps:
Step 1. Copper-nickel ion mixed solution preparation: mixing a copper salt solution
with a nickel salt solution to obtain a copper-nickel ion mixed solution, wherein the
copper salt and the nickel salt are nitrate, sulfate, and chloride, the copper salt and the
nickel salt shall be a same kind of metal salts, and molar ratio of the Cu 2 + and the Ni 2 +
in the copper-nickel ion mixed solution is 1:3 - 3:1;
Step 2. Precursor reaction solution preparation: taking N,N-dimethylformamide
or/and absolute ethyl alcohol with purified water as a solvent, and
1,3,5-benzenetricarboxylic acid as a solute, magnetically stirring evenly to get a
mixed solution containing 1,3,5-benzenetricarboxylic acid with a concentration of
0.1mol/L, then adding 60ml of the mixed solution containing
1,3,5-benzenetricarboxylic acid into 20ml of the copper-nickel ion mixed solution
obtained in the Step 1, and magnetic stirring for 20 min to obtain a precursor reaction
solution;
Step 3. Precursor preparation: putting the precursor reaction solution obtained in the
Step 2 into a reaction still, crystallizing at 90-180 DEG C for 16h and obtaining the
precursor;
Step 4. Impurities removal: immersing the precursor obtained in the Step 3 into
absolute ethyl alcohol for 24h, then centrifuging to remove the absolute ethyl alcohol,
repeatedly immersing and centrifuging for three times, and drying at 60 DEG C to get
a precursor with remnant metal salts and organic ligands removed;
Step 5. Precursor activation treatment: placing the precursor obtained in the Step 4
into a vacuum oven at 160 DEG C for an activation treatment;
Step 6. Precursor vulcanization-carbonization treatment: mixing the activated
precursor obtained in the Step 5 with powdered sulfur of high purification degree at a
molar ratio of 1:1 in a high energy ball-grinding mill for 2h to obtain a mixed
precursor, then placing the mixed precursor into an argon tube furnace to calcine at a
vulcanization-carbonization temperature for 2h, and obtaining the Ni-containing
CuS/C composite material.
Preferably, the molar ratio of Cu2+ and Ni 2 +in the copper-nickel ion mixed solution in
the Step Iis 1:1 ~ 3.
Preferably, purity of the solute 1,3,5-benzenetricarboxylic acid in the Step 2 is 98%.
Further, the solvent in the Step 2 is a mixed solution of N,N-dimethylformamide or
absolute ethyl alcohol with purified water at a volume ratio of 1:1, or a mixed solution
of N,N-dimethylformamide, absolute ethyl alcohol and purified water at a volume
ratio of 1:1:1 - 1:1:5.
Preferably, a volume ratio of N,N-dimethylformamide, absolute ethyl alcohol, and
purified water in the Step 2 is 1:1:5.
Preferably, the precursor in the Step 5 is placed in the vacuum oven at 160 DEG C for a twelve-hour activation treatment.
Preferably, the vulcanization-carbonization temperature in the Step 6 is 350 DEG C
800 DEG C.
Preferably, purity of powdered sulfur in the Step 6 is 99.95%.
Preferably, in the Step 6, the way that the activated precursor and the powdered sulfur
are mixed in the high energy ball-grinding mill is, taking zirconia balls with a particle
size of 5mm and a particle size of1cm as a grinding media, and taking the activated
precursor and the powdered sulfur at a mass ratio of 1:1 as materials, then grinding
the grinding media and the materials at a mass ratio of 20:1 under the protection of
argon, at a speed of 300-500r/min, for 2h to obtain the mixed precursor.
Preferably, in the Step 6, under the protection of argon, the mixed precursor is
obtained after a two-hour ground process at a speed of 500r/min.
The present invention has following beneficial effects:
1. The metal is in situ grown in the carbon frame, and distributed evenly and
uniformly thereon; metal ions of the Ni-containing CuS/C composite material of the
present invention form stable chemical bonds with organic reagents during the
preparation process so as to grow in situ on the carbon frame and are distributed
stably and evenly. Therefore, the present invention solves the problems of uneven
metal distribution, easy agglomeration, poor physical and chemical uniformity, and
poor battery uniformity due to the absence of chemical bonds between the metal and
the carbon when the copper sulfide/carbon composite material is prepared according
to the prior art.
2. Unique porous carbon frame structure: carbon frames in the Ni-containing CuS/C
composite material of the present invention have a unique porous structure which can
provide more active sites for electrochemical reaction. Good conductivity is beneficial
to improving the discharging performance of the cell, and the volume expansion
generated during electrochemical reaction can be inhibited due to carbon frame
constraint in the present invention.
3. Bimetallic ion bonds for fixing sulfur: the Ni-containing CuS/C composite material
of the present invention has copper and nickel bimetallic ionic bonds to fix sulfur, and
the present invention has strong adsorption capacity for polysulfide ions and can
effectively inhibit the shuttling problem of polysulfide ions.
4. Bimetallic ions for volume expansion inhibition: synergistic effects of
nickel-copper bimetallic ions in the Ni-containing CuS/C composite materials of the
present invention are conducive to restrain the volume expansion and improve the
electrochemical performance of the battery.
5. Simple process, environment friendly, and no demands for high temperature and
high pressure: in the process adopted by the present invention pure sulfur can directly
be used as a sulfur source, which is not liable to produce polluting gases and
by-products, and the operation can be completed in ordinary laboratories without high
temperature and high pressure conditions.
Description of Drawings
1. Figure 1 is an XRD diagram of the precursor material obtained in the Step 4 of
Embodiment 1;
2. Figure 2 is an SEM diagram of the precursor material obtained in the Step 4 of
Embodiment 1;
3. Figure 3 is an XRD diagram of the Ni-containing CuS/C composite material
obtained in Embodiment 1;
4. Figure 4 is an SEM diagram of the Ni-containing CuS/C composite material
obtained in Embodiment 1.
Specific Embodiments
The present invention is further described in combination with embodiments below.
Embodiment 1
A preparation method of the Ni-containing CuS/C composite material of the present
invention comprises following steps:
Step 1. Copper-nickel ion mixed solution preparation: mixing a copper nitrate
solution with a nickel nitrate solution to obtain a copper-nickel ion mixed solution,
wherein the molar ratio of Cu2+and Ni2+ in the copper-nickel ion mixed solution is
1:1;
Step 2. Precursor reaction solution preparation: taking a mixture containing
N,N-dimethylformamide, absolute ethyl alcohol and purified water at a volume ratio
of 1:1:5 as a solvent, and taking 1,3,5-benzenetricarboxylic acid of 98% purity as a
solute, magnetic stirring evenly to get a mixed solution containing
1,3,5-benzenetricarboxylic acid with a concentration of 0.1mol/L, then adding 60ml
of the mixed solution containing 1,3,5-benzenetricarboxylic acid into 20ml of the
copper-nickel ion mixed solution obtained in the Step 1, and magnetic stirring for
min to obtain the precursor reaction solution;
Step 3. Precursor preparation: putting the precursor reaction solution obtained in the
Step 2 into a reaction still, crystallizing at 100 DEG C for 16h and obtaining the
precursor;
Step 4. Impurities removal: immersing the precursor obtained in the Step 3 into
absolute ethyl alcohol for 24h, then centrifuging to remove the absolute ethyl alcohol,
repeatedly immersing and centrifuging for 3 times, and drying at 60 DEG C to get the
precursor with remnant metal salts and organic ligands removed;
Step 5. Precursor activation treatment: placing the precursor obtained in the Step 4
into a vacuum oven at 160 DEG C for an activation treatment for 12h;
Step 6. Precursor vulcanization-carbonization treatment: mixing the activated
precursor obtained in the Step 5 with powdered sulfur of 99.95% purity at a molar
ratio of 1:1 in a high energy ball-grinding mill for 2h to obtain a mixed precursor, then
placing the mixed precursor into an argon tube furnace to calcine at a
vulcanization-carbonization temperature of 350 DEG C for 2h, and obtaining the
Ni-containing CuS/C composite material.
Further, in the Step 6, the activated precursor and the powdered sulfur in a high
energy ball-grinding mill are mixed in a way in which zirconia balls with a particle
size of 5mm and a particle size of lcm are used as a grinding media, and the activated
precursor and powdered sulfur at a mass ratio of 1:1 are taken as materials, then the
grinding media and the materials at a mass ratio of 20:1 are ground under the
protection of argon at a speed of 300-500r/min for 2 h to obtain the mixed precursor.
The XRD diagram of the precursor material obtained in Step 4 of this embodiment is
shown as Figure 1, and the ICP-AES results are shown as Table 1, which manifests
the precursor materials obtained in the Step 4 are nickel doped copper based materials,
wherein a primary part thereof are copper based materials , and only a small amount
of nickel based materials are doped.
Table 1: Content of Cu and Ni in Ni - doped Cu - based organic frame material
determined by ICP-AES
Cu Ni
23.2wt% 0.7wt%
The SEM diagram of the precursor material obtained in the Step 4 of the present
embodiment is shown as Figure 2, wherein Figure 2(a) is after 500 times
magnification, and Figure 2(b) is after 5000 times magnification. It can be clearly
seen that the precursor generated in the present invention has a regular octahedral
shape, and average grain size thereof is 25tm.
The XRD diagram of the Ni-containing CuS/C composite material obtained in the
Step 6 of the present embodiment is shown as Figure 3, wherein the peaks in the
figure all correspond to copper sulfide peaks and amorphous carbon peaks, indicating
that the prepared material is a composite material of copper sulfide and carbon;
The SEM diagram of the Ni-containing CuS/C composite material obtained in Step 6
of the present embodiment is shown as Figure 4, wherein Figure 4(a) is after 1000
times magnification and Figure 4(b) is after 5000 times magnification. The average
particle size of the product is 25tm, and regular morphology of the octahedron is
somewhat collapsed, but general morphology of the octahedral block is still
maintained.
Assembly and testing of a lithium battery
Taking the Ni-containing CuS/C composite material obtained in the Step 6 as a
positive electrode and the lithium metal as a negative electrode; a mixture of ethylene
glycol dimethyl ether (DME) and 1, 3-dioxy-pentyl ring (DOL) with a volume ratio of
1:1 as a solvent; 1mol/L lithium trifluoromethyl sulfonate (LiFSO3) electrolyte,
Celgard2400 diaphragm, and assembling with a CR2016 type clunker battery in an
argon atmosphere, using LAND battery test system to test the battery performance;
battery test temperature is a normal temperature, a charging and discharging voltage
range is 1-3V, constant current with a current density of1OOmA/g is used to charge
and discharge, the number of cycles is 50, as shown in Table 2, cyclic reversible
capacity of the Ni-containing CuS/C composite material is 1036mAh/g.
Embodiment 2
A preparation method of the Ni-containing CuS/C composite material of the present
invention comprises following steps:
Step1. Copper-nickel ion mixed solution preparation: mixing a copper nitrate solution
with a nickel nitrate solution to obtain a copper-nickel ion mixed solution wherein the
molar ratio of Cu2+ and Ni2 + in the copper-nickel ion mixed solution is 1:3;
Step2. precursor reaction solution preparation: taking a mixture containing
N,N-dimethylformamide, absolute ethyl alcohol and purified water at a volume ratio
of 1:1:1 as a solvent, and 1,3,5-benzenetricarboxylic acid of 98% purity as a solute,
magnetic stirring evenly to get a mixed solution containing 1,3,5-benzenetricarboxylic
acid of 0.1mol/L, then adding 60ml of the mixed solution containing
1,3,5-benzenetricarboxylic acid into 20ml of the copper-nickel ion mixed solution
obtained in the Step 1, and magnetic stirring for 20 min to obtain a precursor reaction
solution;
Step3. Precursor preparation: putting the precursor reaction solution obtained in the
Step 2 into a reaction still, crystallizing at 90 DEG C for 16h and obtaining a
precursor;
Step4. Impurities removal: immersing the precursor obtained in the Step 3 into
absolute ethyl alcohol for 24h, then centrifuging to remove the absolute ethyl alcohol,
repeatedly immersing and centrifuging for 3 times, and drying at 60 DEG C to get a
precursor with remnant metal salts and organic ligands removed;
Step5. Precursor activation treatment: placing the precursor obtained in the Step 4 into
a vacuum oven at 160 DEG C for an activation treatment for 12h;
Step6. Precursor vulcanization-carbonization treatment: mixing the activated
precursor obtained in the Step 5 with powdered sulfur of 99.95% purity at a molar
ratio of 1:1 in a high energy ball-grinding machine for 2h to obtain a mixed precursor,
then placing the mixed precursor into an argon tube furnace to calcine at a
vulcanization-carbonization temperature of 350 DEG C for 2h, and obtaining a
Ni-containing CuS/C composite material.
Further, in the Step 6, the activated precursor and the powdered sulfur in the high
energy ball-grinding machine are mixed in a way in which zirconia balls with a
particle size of 5mm and zirconia balls with a particle size of lcm at a mass ratio of
1:1 are used as a grinding media, and the activated precursor and the powdered sulfur
at a molar ratio of 1:1 are taken as materials, then the grinding media and the
materials are ground at a mass ratio of 20:1 under the protection of argon at a speed of
450r/min for 2h to obtain the mixed precursor.
The test method adopted of the present embodiment is consistent with that of the embodiment 1, and the specific characterization is shown in Table 2, wherein phase characterization proves the existence of CuS and S; SEM morphology shows that an average particle size is 26tm, and morphology of octahedron; and the cyclic reversible capacity was 989mAh/g after 50 cycles of LAND Electrochemical Performance Test.
Embodiment 3 A preparation method of the Ni-containing CuS/C composite material of the present invention comprises following steps: Step 1. Copper-nickel ion mixed solution preparation: mixing a copper nitrate solution with a nickel nitrate solution to obtain a copper-nickel ion mixed solution, wherein the molar ratio of Cu2+ and Ni2+ in the copper-nickel ion mixed solution is 1:3; Step 2. Precursor reaction solution preparation: taking a mixture containing absolute ethyl alcohol and purified water at a volume ratio of 1:1 as a solvent, and 1,3,5-benzenetricarboxylic acid of 98% purity as a solute, magnetic stirring evenly to get a mixed solution containing 1,3,5-benzenetricarboxylic acid of 0.1mol/L, then adding 60ml of the mixed solution containing 1,3,5-benzenetricarboxylic acid into ml of the copper-nickel ion mixed solution obtained in the Step 1, and magnetic stirring for 20min to obtain the precursor reaction solution; Step 3. Precursor preparation: putting the precursor reaction solution obtained in the Step2 into a reaction still, crystallizing at 100 DEG C for 16 h and obtaining a precursor; Step 4. Impurities removal: immersing the precursor obtained in the Step 3 into absolute ethyl alcohol for 24h, then centrifuging to remove the absolute ethyl alcohol, repeatedly immersing and centrifuging for 3 times, and drying at 60 DEG C to get a precursor with remnant metal salts and organic ligands removed; Step 5. Precursor activation treatment: placing the precursor obtained in the Step 4 into a vacuum oven at 160 DEG C for an activation treatment for 12h;
Step 6. Precursor vulcanization-carbonization treatment: mixing the activated
precursor obtained in the Step 5 with powdered sulfur of 99.95% purity at a molar
ratio of 1:1 in a high energy ball-grinding machine for 2h to obtain a mixed precursor,
then placing the mixed precursor into an argon tube furnace to calcine at a
vulcanization-carbonization temperature of 500 DEG C for 2h, and obtaining the
Ni-containing CuS/C composite material.
Further, in the Step 6, the activated precursor and the powdered sulfur in the high
energy ball-grinding machine are mixed in a way in which zirconia balls with a
particle size of 5mm and zirconia balls with a particle size of 1cm at a mass ratio of
1:1 are used as a grinding media, and the activated precursor and powdered sulfur at a
molar ratio of 1:1 are taken as materials, then the grinding media and the materials are
ground at a mass ratio of 20:1 under the protection of argon at a speed of 400r/min for
2h to obtain the mixed precursor.
The test method adopted in the present embodiment is consistent with that in the
Embodiment 1, and the specific characterization is shown in Table 2, wherein phase
characterization proves the existence of Cui. 8S and S; SEM morphology is
characterized as being rod-like, with an average length of 28pm; and the cyclic
reversible capacity is 897mAh/g after 50 cycles of LAND Electrochemical
Performance Test.
Embodiment 4
A preparation method of the Ni-containing CuS/C composite material of the present
invention comprises following steps:
Step 1. Copper-nickel ion mixed solution preparation: mixing a copper nitrate solution
with a nickel nitrate solution to obtain a copper-nickel ion mixed solution wherein the
molar ratio of Cu 2+ and Ni2 +in the copper-nickel ion mixed solution is 3:1;
Step 2. Precursor reaction solution preparation: taking a mixture of absolute ethyl
alcohol and purified water at a volume ratio of 1:1 as a solvent, and
1,3,5-benzenetricarboxylic acid of 98% purity as a solute, magnetic stirring evenly to get a mixed solution containing 1,3,5-benzenetricarboxylic acid of 0.1mol/L, then adding 60ml of the mixed solution containing 1,3,5-benzenetricarboxylic acid into ml of the copper-nickel ion mixed solution obtained in the Step 1, and magnetic stirring for 20 min to obtain the precursor reaction solution;
Step 3. Precursor preparation: putting the precursor reaction solution obtained in the
Step2 into a reaction still, crystallizing at 130 DEG C for 16h and obtaining a
precursor;
Step 4. Impurities removal: immersing the precursor obtained in the Step 3 into
absolute ethyl alcohol for 24h, then centrifuging to remove the absolute ethyl alcohol,
repeatedly immersing and centrifuging for 3 times, and drying at 60 DEG C to get a
precursor with remnant metal salts and organic ligands removed;
Step 5. Precursor activation treatment: placing the precursor obtained in the Step 4
into a vacuum oven at 160 DEG C for an activation treatment for 12h;
Step 6. Irecursor vulcanization-carbonization treatment: mixing the activated
precursor obtained in the Step 5 with powdered sulfur of 99.95% purity at a molar
ratio of 1:1 in a high energy ball-grinding machine for 2h to obtain a mixed precursor,
then placing the mixed precursor into an argon tube furnace to calcine at a
vulcanization-carbonization temperature of 500 DEG C for 2h, and obtaining a
Ni-containing CuS/C composite material.
Further, in the Step 6, the activated precursor and the powdered sulfur in the high
energy ball-grinding machine are mixed in a way in which zirconia balls with a
particle size of 5mm and zirconia balls with a particle size of lcm at a mass ratio of
1:1 are used as a grinding media, and the activated precursor and powdered sulfur at a
molar ratio of 1:1 are taken as materials, then the grinding media and the materials are
ground at a mass ratio of 20:1 under the protection of argon at a speed of 400r/min for
2h to obtain the mixed precursor.
The test method adopted in the present embodiment is consistent with that in the
Embodiment 1, and the specific characterization is shown in Table 2, wherein phase
characterization proves the existence of Cui. 8S and S; SEM morphology is characterized as morphology of an octahedron, with an average particle size of 32pm; and the cyclic reversible capacity is 876mAh/g after 50 cycles of LAND
Electrochemical Performance Test.
Embodiment 5
A preparation method of the Ni-containing CuS/C composite material of the present
invention comprises following steps:
Step 1. Copper-nickel ion mixed solution preparation: mixing a copper nitrate solution
with a nickel nitrate solution to obtain a copper-nickel ion mixed solution wherein the
molar ratio of Cu2+ and Ni2 + in the copper-nickel ion mixed solution is 3:1;
Step 2. Precursor reaction solution preparation: taking a N,N-dimethylformamide as a
solvent, and 1,3,5-benzenetricarboxylic acid of 98% purity as a solute, magnetic
stirring evenly to get a mixed solution containing 1,3,5-benzenetricarboxylic acid of
0.1mol/L, then adding 60ml of the mixed solution containing
1,3,5-benzenetricarboxylic acid into 20ml of the copper-nickel ion mixed solution
obtained in the Step 1, and magnetic stirring for 20min to obtain the precursor
reaction solution;
Step 3. Precursor preparation: putting the precursor reaction solution obtained in the
Step 2 into a reaction still, crystallizing at 180 DEG C for 16h and obtaining the
precursor;
Step 4. Impurities removal: immersing the precursor obtained in the Step 3 into
absolute ethyl alcohol for 24h, then centrifuging to remove the absolute ethyl alcohol,
repeatedly immersing and centrifuging for 3 times, and drying at 60 DEG C to get a
precursor with remnant metal salts and organic ligands removed;
Step 5. Precursor activation treatment: placing the precursor obtained in the Step 4
into a vacuum oven at 160 DEG C for an activation treatment for 12h;
Step 6. Precursor vulcanization-carbonization treatment: mixing the activated
precursor obtained in the Step 5 with powdered sulfur of 99.95% purity at a molar
ratio of 1:1 in a high energy ball-grinding machine for 2h to obtain a mixed precursor,
then placing the mixed precursor into an argon tube furnace to calcine at a vulcanization-carbonization temperature of 800 DEG C for 2h, and obtaining the
Ni-containing CuS/C composite material.
Further, in the Step 6, the activated precursor and the powdered sulfur in the high
energy ball-grinding machine are mixed in a way in which zirconia balls with a
particle size of 5mm and zirconia balls with a particle size of lcm at a mass ratio of
1:1 are used as a grinding media, and the activated precursor and the powdered sulfur
at a molar ratio of 1:1 are taken as materials, then the grinding media and the
materials are ground at a mass ratio of 20:1 under the protection of argon at a speed of
500r/min for 2h to obtain the mixed precursor.
The test method adopted in the present embodiment is consistent with that in the
Embodiment 1, and the specific characterization is shown in Table 2, wherein phase
characterization proves the existence of CuS and S; SEM morphology is characterized
as morphology of an octahedron, with an average particle size of 35pm; and the cyclic
reversible capacity is 517mAh/g after 50 cycles of LAND Electrochemical
Performance Test.
Embodiment 6
A preparation method of the Ni-containing CuS/C composite material of the present
invention comprises following steps:
Step 1. Copper-nickel ion mixed solution preparation: mixing a copper nitrate solution
with a nickel nitrate solution to obtain a copper-nickel ion mixed solution wherein the
molar ratio of Cu2+ and Ni2 +in the copper-nickel ion mixed solution is 1:1;
Step 2. Precursor reaction solution preparation: taking a mixture of absolute ethyl
alcohol and purified water at a volume ratio of 1:1 as a solvent, and
1,3,5-benzenetricarboxylic acid of 98% purity as a solute, magnetic stirring evenly to
get a mixed solution containing 1,3,5-benzenetricarboxylic acid of 0.1mol/L, then
adding 60ml of the mixed solution containing 1,3,5-benzenetricarboxylic acid into
ml of the copper-nickel ion mixed solution obtained in the Step 1, and magnetic
stirring for 20 min to obtain a precursor reaction solution;
Step 3. Precursor preparation: putting the precursor reaction solution obtained in the
Step 2 into a reaction still, crystallizing at 90 DEG C for 16h and obtaining a
precursor;
Step 4. Impurities removal-immersing the precursor obtained in the Step 3 into
absolute ethyl alcohol for 24h, then centrifuging to remove the absolute ethyl alcohol,
repeatedly immersing and centrifuging for 3 times, and drying at 60 DEG C to get a
precursor with remnant metal salts and organic ligands removed;
Step 5. Precursor activation treatment: placing the precursor obtained in the Step 4
into vacuum oven at 160 DEG C for an activation treatment for 12h;
Step 6. Precursor vulcanization-carbonization treatment: mixing the activated
precursor obtained in the Step 5 with powdered sulfur of 99.95% purity at a molar
ratio of 1:1 in a high energy ball-grinding machine for 2h to obtain a mixed precursor,
then placing the mixed precursor into an argon tube furnace to calcine at a
vulcanization-carbonization temperature of 350 DEG C for 2h, and obtaining the
Ni-containing CuS/C composite material.
Further, in the Step 6, the activated precursor and the powdered sulfur in the high
energy ball-grinding machine are mixed in a way in which zirconia balls with a
particle size of 5mm and zirconia balls with a particle size of lcm at a mass ratio of
1:1 are used as a grinding media, and the activated precursor and powdered sulfur at a
molar ratio of 1:1 are taken as materials, then the grinding media and the materials are
ground at a mass ratio of 20:1 under the protection of argon at a speed of 300r/min for
2h to obtain the mixed precursor.
The test method adopted in the present embodiment is consistent with that in the
Embodiment 1, and the specific characterization is shown in Table 2, wherein phase
characterization proves the existence of CuS and S; SEM morphology is characterized
as being rod-like, with an average length of 25pm; and the cyclic reversible capacity
is 945mAh/g after 50 cycles of LAND Electrochemical Performance Test.
Embodiment 7
A preparation method of the Ni-containing CuS/C composite material of the present
invention comprises following steps:
Step 1. Copper-nickel ion mixed solution preparation: mixing a copper nitrate solution
with a nickel nitrate solution to obtain a copper-nickel ion mixed solution wherein the
molar ratio of Cu2+ and Ni2 + in the copper-nickel ion mixed solution is 1:1;
Step 2. Precursor reaction solution preparation: taking a mixture containing
N,N-dimethylformamide, absolute ethyl alcohol and purified water at a volume ratio
of 1:1:5 as a solvent, and 1,3,5-benzenetricarboxylic acid of 98% purity as a solute,
magnetic stirring evenly to get a mixed solution containing 1,3,5-benzenetricarboxylic
acid of 0.1mol/L, then adding 60ml of the mixed solution containing
1,3,5-benzenetricarboxylic acid into 20ml of the copper-nickel ion mixed solution
obtained in the Step 1, and magnetic stirring for 20 min to obtain a precursor reaction
solution;
Step 3. Precursor preparation: putting the precursor reaction solution obtained in the
Step 2 into a reaction still, crystallizing at 100 DEG C for 16h and obtaining a
precursor;
Step 4. Impurities removal: immersing the precursor obtained in the Step 3 into
absolute ethyl alcohol for 24h, then centrifuging to remove the absolute ethyl alcohol,
repeatedly immersing and centrifuging for 3 times, and drying at 60 DEG C to get a
precursor with remnant metal salts and organic ligands removed;
Step 5. Precursor activation treatment: placing the precursor obtained in the Step 4
into a vacuum oven at 160 DEG C for an activation treatment for 12h;
Step 6. Precursor vulcanization-carbonization treatment: mixing the activated
precursor obtained in the Step 5 with powdered sulfur of 99.95% purity at a molar
ratio of 1:1 in a high energy ball-grinding machine for 2h to obtain a mixed precursor,
then placing the mixed precursor into an argon tube furnace to calcine at a
vulcanization-carbonization temperature of 500 DEG C for 2h, and obtaining the
Ni-containing CuS/C composite material.
Further, in the Step 6, the activated precursor and the powdered sulfur in the high
energy ball-grinding machine are mixed in a way in which zirconia balls with a particle size of 5mm and zirconia balls with a particle size of lcm at a mass ratio of
1:1 are used as a grinding media, and the activated precursor and powdered sulfur at a
molar ratio of 1:1 are taken as materials, then the grinding media and the materials are
ground at a mass ratio of 20:1 under the protection of argon at a speed of 300r/min for
2 h to obtain the mixed precursor.
The test method adopted in the present embodiment is consistent with that in the
Embodiment 1, and the specific characterization is shown in Table 2, wherein phase
characterization proves the existence of Cui.SS and S; SEM morphology is
characterized as morphology of an octahedron, with an average particle size of 29tm;
and the cyclic reversible capacity is 679mAhg after 50 cycles of LAND
Electrochemical Performance Test.
Embodiment 8
A preparation method of the Ni-containing CuS/C composite material of the present
invention comprises following steps:
Step 1. Copper-nickel ion mixed solution preparation: mixing a copper nitrate solution
with a nickel nitrate solution to obtain a copper-nickel ion mixed solution wherein the
molar ratio of Cu2+ and Ni2 +in the copper-nickel ion mixed solution is 1:1;
Step 2. Precursor reaction solution preparation: taking a N,N-dimethylformamide as a
solvent, and 1,3,5-benzenetricarboxylic acid of 98% purity as a solute, magnetic
stirring evenly to get a mixed solution containing 1,3,5-benzenetricarboxylic acid of
0.1mol/L, then adding 60ml of the mixed solution containing
1,3,5-benzenetricarboxylic acid into 20ml of the copper-nickel ion mixed solution
obtained in the Step 1, and magnetic stirring for 20min to obtain a precursor reaction
solution;
Step 3. Precursor preparation: putting the precursor reaction solution obtained in the
Step 2 into a reaction still, crystallizing at 130 DEG C for 16h and obtaining a
precursor;
Step 4. Impurities removal: immersing the precursor obtained in the Step 3 into absolute ethyl alcohol for 24h, then centrifuging to remove the absolute ethyl alcohol, repeatedly immersing and centrifuging for 3 times, and drying at 60 DEG C to get a precursor with remnant metal salts and organic ligands removed;
Step 5. Precursor activation treatment: placing the precursor obtained in the Step 4
into vacuum oven at 160 DEG C for an activation treatment for 12h;
Step 6. Precursor vulcanization-carbonization treatment: mixing the activated
precursor obtained in the Step 5 with powdered sulfur of 99.95% purity at a molar
ratio of 1:1 in a high energy ball-grinding machine for 2h to obtain a mixed precursor,
then placing the mixed precursor into an argon tube furnace to calcine at a
vulcanization-carbonization temperature of 800 DEG C for 2h, and obtaining the
Ni-containing CuS/C composite material.
Further, in the Step 6, the activated precursor and the powdered sulfur in the high
energy ball-grinding machine are mixed in a way in which zirconia balls with a
particle size of 5mm and zirconia balls with a particle size of 1cm at a mass ratio of
1:1 are used as a grinding media, and the activated precursor and powdered sulfur at a
molar ratio of 1:1 are taken as materials, then grinding media and materials are
ground at a mass ratio of 20:1 under the protection of argon at a speed of 300r/min for
2h to obtain the mixed precursor.
The test method adopted in the present embodiment is consistent with that in the
Embodiment 1, and the specific characterization is shown in Table 2, wherein phase
characterization proves the existence of Cu 2 S and S; SEM morphology is
characterized as morphology of an octahedron, with an average particle size of 33pm;
and the cyclic reversible capacity is 757mAh/g after 50 cycles of LAND
Electrochemical Performance Test.
Embodiment 9
A preparation method of the Ni-containing CuS/C composite material of the present
invention comprises following steps:
Step 1. Copper-nickel ion mixed solution preparation: mixing a copper nitrate solution with a nickel nitrate solution to obtain a copper-nickel ion mixed solution wherein the molar ratio of Cu2+ and Ni2 +in the copper-nickel ion mixed solution is 1:1;
Step 2. Precursor reaction solution preparation: taking a N,N-dimethylformamide as a
solvent, and 1,3,5-benzenetricarboxylic acid of 98% purity as a solute, magnetic
stirring evenly to get a mixed solution containing 1,3,5-benzenetricarboxylic acid of
0.1mol/L, then adding 60ml of the mixed solution containing
1,3,5-benzenetricarboxylic acid into 20ml of the copper-nickel ion mixed solution
obtained in the Step 1, and magnetic stirring for 20min to obtain a precursor reaction
solution;
Step 3. Precursor preparation: putting the precursor reaction solution obtained in the
Step 2 into a reaction still, crystallizing at 180 DEG C for 16h and obtaining a
precursor;
Step 4. Impurities removal: immersing the precursor obtained in the Step 3 into
absolute ethyl alcohol for 24h, then centrifuging to remove the absolute ethyl alcohol,
repeatedly immersing and centrifuging for 3 times, and drying at 60 DEG C to get a
precursor with remnant metal salts and organic ligands removed;
Step 5. Precursor activation treatment: placing the precursor obtained in the Step 4
into vacuum oven at 160 DEG C for an activation treatment for 12h;
Step 6. Precursor vulcanization-carbonization treatment: mixing the activated
precursor obtained in the Step 5 with powdered sulfur of 99.95% purity at a molar
ratio of 1:1 in a high energy ball-grinding machine for 2h to obtain a mixed precursor,
then placing the mixed precursor into an argon tube furnace to calcine at a
vulcanization-carbonization temperature of 500 DEG C for 2h, and obtaining the
Ni-containing CuS/C composite material.
Further, in the Step 6, the activated precursor and the powdered sulfur in the high
energy ball-grinding machine are mixed in a way in which zirconia balls with a
particle size of 5mm and zirconia balls with a particle size of 1cm at a mass ratio of
1:1 are used as a grinding media, and the activated precursor and powdered sulfur at a
molar ratio of 1:1 are taken as materials, then the grinding media and the materials are
ground at a mass ratio of 20:1 under the protection of argon at a speed of 300r/min for
2h to obtain the mixed precursor.
The test method adopted in the present embodiment is consistent with that in the
Embodiment 1, and the specific characterization is shown in Table 2, wherein phase
characterization proves the existence of Cu2 S and S; SEM morphology is
characterized as morphology of an octahedron, with an average particle size of 30pm;
and the cyclic reversible capacity is 765mAh/g after 50 cycles of LAND
Electrochemical Performance Test.
Embodiment 10
Effects of grinding methods on material properties
A preparation method of the Ni-containing CuS/C composite material of the present
invention comprises following steps:
Step 1. Copper-nickel ion mixed solution preparation: mixing a copper nitrate solution
with a nickel nitrate solution to obtain a copper-nickel ion mixed solution wherein the
molar ratio of Cu 2+ and Ni2 + in the copper-nickel ion mixed solution is 1:1;
Step 2. Precursor reaction solution preparation: taking a mixture containing
N,N-dimethylformamide, absolute ethyl alcohol and purified water at a volume ratio
of 1:1:5 as a solvent, and 1,3,5-benzenetricarboxylic acid of 98% purity as a solute,
magnetic stirring evenly to get a mixed solution containing 1,3,5-benzenetricarboxylic
acid of 0.1mol/L, then adding 60ml of the mixed solution containing
1,3,5-benzenetricarboxylic acid into 20ml of the copper-nickel ion mixed solution
obtained in the Step 1, and magnetic stirring for 20 min to obtain the precursor
reaction solution;
Step 3. Precursor preparation: putting the precursor reaction solution obtained in the
Step 2 into a reaction still, crystallizing at 100 DEG C for 16h and obtaining the
precursor;
Step 4. Impurities removal: immersing the precursor obtained in the Step 3 into
absolute ethyl alcohol for 24h, then centrifuging to remove the absolute ethyl alcohol,
repeatedly immersing and centrifuging for 3 times, and drying at 60 DEG C to get a precursor with remnant metal salts and organic ligands removed;
Step 5. Precursor activation treatment: placing the precursor obtained in the Step4 into
a vacuum oven at 160 DEG C for an activation treatment for 12h;
Step 6. Precursor vulcanization-carbonization treatment: mixing the activated
precursor obtained in the Step 5 with powdered sulfur of 99.95% purity at a molar
ratio of 1:1 in a mortar to manually grind for 10 min.
The test method adopted in the present embodiment is consistent with that in the
Embodiment 1, and specific characterization is shown in Table 2, wherein phase
characterization proves the existence of CuS and S; SEM morphology is characterized
as morphology of an octahedron, with an average particle size of 25pm; and the cyclic
reversible capacity is 679mAh/g after 50 cycles of LAND Electrochemical
Performance Test.
Embodiment 11
A preparation method of the Ni-containing CuS/C composite material of the present
invention comprises following steps:
Step 1. Precursor reaction solvent preparation: dissolving 3g of cupric nitrate
trihydrate and 2g of trimellitic anhydride into 100 ml of a solvent which contains
N,N-dimethylformamide, ethyl alcohol and H 2 0 at a volume ratio of 1:1:1;
Step 2: Precursor preparation: heating at 105DEG C for 12 hour;
Step 3: Removal of the precursor reaction solvent: immersing in methanol twice a day
for several days;
Step 4: Precursor activation treatment: degassing at a vacuum of 170 DEG C for 18
hour;
Step 5: Precursor activation treatment: separately placing and heating the obtained
precursors and powdered sulfur into an argon tube furnace to calcine at a
vulcanization-carbonization temperature of 350 DEG C for 2h
The Ni-containing CuS/C composite material obtained in the present embodiment is
of an octahedral morphology and the cyclic reversible capacity is 495mAh/g after 50 cycles of LAND Electrochemical Performance Test.
Comparison of composite material test results in Embodiments 1-11
Table 2: Phase, average crystal grain, morphology and electrochemical cycle
performance test results of electrode materials composed of sulfur-copper compounds
Average 50Cycle
Phase crystal grain Morphology Discharging
(pm) Capacity
Embodiment 1 Cu2 S, S 25 octahedron 1036
Embodiment 2 Cu2 S, S 26 octahedron 989
Embodiment 3 Cui.8S, S 28(length of rodlike 897
rod)
Embodiment 4 Cu1.8 S, S 32 octahedron 876
Embodiment 5 Cu2S, CuO, S 35 octahedron 517
Embodiment 6 CuS, S 25(length of rodlike 945
rod)
Embodiment 7 Cu 1.8 S, S 29 octahedron 679
Embodiment 8 Cu2 S, S 33 octahedron 757
Embodiment 9 Cu2 S, S 30 octahedron 765
Embodiment 10 CuS, S 25 octahedron 305
Embodiment 11 CuS 30 octahedron 495
It can be seen from Table 2 that by adopting the preparation method of the present
invention, the electrochemical performance of the sulfur-copper compound after
nickel is introduced can be more than twice as good as the pure copper-sulfur
compound; in the Embodiment 10, carbon materials with nickel and copper ions are
also prepared, but due to manual grinding and no high-temperature carbonization, the
electrical conductivity thereof is poor, and the metal ions have strong activity and are
liable to lose, and the electrochemical performance thereof is the worst; and in the
Embodiment 11, nickel ion doping has not been introduced, resulting in volume
expansion of the material, pulverization of the electrode material, and poor
electrochemical performances.
Table 3: Comparison of experimental conditions in Embodiments1-11
Crystalliz Crystalliza Copper ation/ tion/ and Vulcaniz Vulcanizat Ball-Grinding Embodiment nickel ion Solvent ation ion/ Speed concentra Temperat Ball-Grind tion ure ing Time
molar N,N-dimethylformamide, ratio of 100°C/35 absolute ethyl alcohol and Embodiment Cu2+and 16h/2h/2h 500r/min 0°C purified water at a volume 2 Ni +
ratio of 1:1:5 1:1
molar N,N-dimethylformamide, ratio of 90°C/350 absolute ethyl alcohol and Embodiment2 Cu2 +and 16h/2h/2h 450r/min °C purified water at a volume 2 Ni +
ratio of 1:1:1 1:3
molar
ratio of absolute ethyl alcohol and 100°C/50 Embodiment3 Cu2 + and 16h/2h/2h 400r/min purified water at a volume 0°C Ni 2 + ratio of 1:1
1:3
130°C/50 molar absolute ethyl alcohol and Embodiment4 16h/2h/2h 400r/min 0°C ratio of purified water at a volume
Cu2 and ratio of 1:1 2 Ni
+ 3:1
molar
ratio of 180°C/80 Embodiment Cu2 +and 16h/2h/2h 500r/min N,N-dimethylformamide OOC Ni 2 +
3:1
molar
ratio of absolute ethyl alcohol and 90°C/350 Embodiment6 Cu2 + and 16h/2h/2h 300r/min purified water at a volume °C Ni 2 + ratio of 1:1
1:1
molar N,N-dimethylformamide, ratio of 100°C/50 absolute ethyl alcohol and Embodiment7 Cu2 +and 16h/2h/2h 300r/min 0°C purified water at a volume 2 Ni +
ratio of 1:1:5 1:1
molar
ratio of 130°C/80 Embodiment8 Cu2 +and 16h/2h/2h 300r/min N,N-dimethylformamide OC 2 Ni +
1:1
molar
ratio of 180°C/50 Embodiment9 Cu2 +and 16h/2h/2h 300r/min N,N-dimethylformamide OOC 2 Ni +
1:1
Embodiment 100°C/no molar 16h/none/2 none N,N-dimethylformamide,
0 ne ratio of h absolute ethyl alcohol and
Cu 2+and purified water at a volume
Ni 2 + ratio of 1:1:5
1:1
N,N-dimethylformamide, cupric Embodiment 105°C/35 16h/2h/no ethyl alcohol and purified nitrate none 1 0°C ne water at a volume ratio of trihydrate 1:1:1
It can be seen from Embodiment 1-11 that the crystallization and vulcanization
temperature, the solution composition and concentration, the crystallization and ball
grinding time or the solvent type in the experimental conditions are related to the
electrochemical performance of the composite material finally obtained. Any changes
on the experimental conditions make the physical and chemical properties of the
material change, and the physical and chemical properties of the material determine
the electrochemical properties thereof. As can be seen from summary of experimental
conditions in Table 3, when the crystallization temperature is higher and the
crystallization time is longer, the grain size will be larger, the specific surface area
lower, the surface activation energy lower, and the discharge capacity somehow lower.
In the Embodiments 3, 4, and 6, N,N-dimethylformamide is not used, only water and
ethanol are used, rod-like structure is liable to form, and tap density and porosity of
this two-dimensional rod-like structure is not as good as octahedral structures. In
other embodiments, by adding the solvent containing N,N-dimethylformamide an
octahedral morphology structure is formed, which has a higher tap density, thereby
increasing the capacity of the battery; the porous structure can improve the wettability
of electrolyte, and improvement of a liquid retention ability of the electrode materials
is conducive to improvement of cycle performances of the battery. In the
embodiments 1-5: when the ball milling time is longer, the rotational speed higher, the
grain size of the material will become smaller, the surface area larger, sites available for reaction on the surface more active, and the electrochemical performance better; in
Embodiments 4 and 5, a concentration of the copper ions relative to a concentration of
the nickel ions is higher, which is conducive to formation of cuprous sulfide Cu2S
phase, whose theoretical specific capacity is lower than the copper sulfide CuS phase,
so the discharging capacity of the battery is reduced; the higher the vulcanization and
carbonization temperature is, the longer the vulcanization and carbonization time is,
the more sulfur powder in the material is lost, so the discharging capacity of the
battery is lower, such as in embodiments 5 and 8. After a comprehensive comparison
of the foregoing experimental conditions, the experimental conditions of Embodiment
1 are selected as an optimal combination. When the Ni-containing CuS/C composite
material prepared according to the technical solution in Embodiment 1 is used as the
positive electrode of lithium-sulfur batteries, a significant outcome of 1036mAh/g
discharging capacity after 50 cycles is achieved.
The application field of the present invention is a lithium-sulfur battery cathode
material, and it is necessary to suppress the ion shuttle effect in the lithium-sulfur
battery. The Ni-containing CuS/C composite material in the present invention can
effectively fix sulfur chemically by copper sulfide and absorb polysulfide ions with
bimetallic elements, effectively address the problem such as polysulfur shuttling,
volume expansion, capacity attenuation and uneven morphology, improve
conductivity of the material, and comprehensively improve energy storage properties
of lithium-sulfur batteries.
The Ni-containing CuS/C composite material of the present invention has following
physical and chemical properties: the peaks in the figures all correspond to copper
sulfide peaks and amorphous carbon peaks, indicating that the prepared material is a
composite of copper sulfide and carbon; the precursor produced according to the
invention has a regular octahedral shape, average grain size thereof is 2 5 pm, and an
average particle size of the sulfide product is 25pm, the shape thereof is like a regular
morphology of the octahedron collapsed to some extent, but an approximate morphology of the octahedron block is still maintained, and morphology and size thereof are evenly distributed. And the electrochemical property of the Ni-containing
CuS/C composite material according to the present invention is that when charging
and discharging at a constant current with a current density of 100mA/g, the cyclic
reversible capacity of the Ni-containing CuS/C composite material after 50 cycles is
1036mAh/g, which shows good structural stability.
Compared with loading metal sulfide on other carbon materials, the method of in-situ
generating carbon frame on CuS according to the present invention makes distribution
of CuS and carbon frame more uniform and bonding at material interfaces more
compact; in the present invention a three-dimensional carbon frame structure can be
formed, which on one hand, increases electronic conductivity of the material, on the
other hand, improves a specific surface area to increase wettability of the interface
electrolyte. In the present invention a hole size of the carbon structure can be
regulated, so that the surface area can be effectively regulated; due to introduction of a
small amount of nickel metal in the copper sulfide, agglomeration of copper ions in
the precursor is inhibited, and volume expansion during electrochemical process of
the electrode material is hindered by synergistic action of the bimetallic.
It is evident to persons skilled in the field that the present invention is not limited to
the details of the above exemplary embodiments and can be realized in other concrete
forms without deviating from the spirit or basic characteristics of the present
invention. Therefore, the embodiments shall in any respect be considered to be
exemplary and non-restrictive, and the scope of the present invention is limited by the
appended claims and not by the foregoing description. It is therefore intended to
include in the present invention all variations which fall within the meaning and scope
of the equivalent requirements of the claim. No appended drawing mark in any claim
shall be construed as limiting the claims in question.
In addition, it should be understood that although the present specification is described in accordance with the embodiments, not each embodiment only contains an independent technical solution. This narration in the specification is only for the sake of clarity, and those skilled in the art should regard the specification as a whole, the technical solutions in the embodiments can also be appropriately combined to form other implementations that can be understood by those skilled in the art.
Claims (10)
1. A preparation method of a Ni-containing CuS/C composite material comprising
following steps:
Step 1. Copper-nickel ion mixed solution preparation: mixing a copper salt solution
with a nickel salt solution to obtain a copper-nickel ion mixed solution, wherein the
copper salt and the nickel salt are nitrate, sulfate, and chloride, the copper salt and the
nickel salt shall be a same kind of metal salts, and molar ratio of the Cu2+ and the Ni2+
in the copper-nickel ion mixed solution is 1:3 - 3:1;
Step 2. Precursor reaction solution preparation: taking N,N-dimethylformamide
or/and absolute ethyl alcohol with purified water as a solvent, and
1,3,5-benzenetricarboxylic acid as a solute, magnetically stirring evenly to get a
mixed solution containing 1,3,5-benzenetricarboxylic acid with a concentration of
0.1mol/L, then adding 60ml of the mixed solution containing
1,3,5-benzenetricarboxylic acid into 20ml of the copper-nickel ion mixed solution
obtained in the Step 1, and magnetic stirring for 20 min to obtain a precursor reaction
solution;
Step 3. Precursor preparation: putting the precursor reaction solution obtained in the
Step 2 into a reaction still, crystallizing at 90-180 DEG C for 16h and obtaining the
precursor;
Step 4. Impurities removal: immersing the precursor obtained in the Step 3 into
absolute ethyl alcohol for 24h, then centrifuging to remove the absolute ethyl alcohol,
repeatedly immersing and centrifuging for three times, and drying at 60 DEG C to get
a precursor with remnant metal salts and organic ligands removed;
Step 5. Precursor activation treatment: placing the precursor obtained in the Step 4
into a vacuum oven at 160 DEG C for an activation treatment;
Step 6. Precursor vulcanization-carbonization treatment: mixing the activated
precursor obtained in the Step 5 with powdered sulfur of high purification degree at a
molar ratio of 1:1 in a high energy ball-grinding mill for 2h to obtain a mixed
precursor, then placing the mixed precursor into an argon tube furnace to calcine at a vulcanization-carbonization temperature for 2h, and obtaining the Ni-containing
CuS/C composite material.
2. The preparation method of a Ni-containing CuS/C composite material according to
claim 1, wherein the molar ratio of Cu2+ and Ni2 + in the copper-nickel ion mixed
solution in the Step 1 is 1:1 ~ 3.
3. The preparation method of a Ni-containing CuS/C composite material according to
claim 1, wherein a purity of solute 1,3,5-benzenetricarboxylic acid in the Step 2 is
98%.
4. The preparation method of a Ni-containing CuS/C composite material according to
claim 1, wherein the solvent in the Step 2 is a mixed solution of
N,N-dimethylformamide or absolute ethyl alcohol with purified water at a volume
ratio of 1:1, or a mixed solution of N,N-dimethylformamide and absolute ethyl
alcohol with purified water at a volume ratio of 1:1:1 - 1:1:5.
5. The preparation method of a Ni-containing CuS/C composite material according to
claim 1, wherein a volume ratio of N,N-dimethylformamide, absolute ethyl alcohol,
and purified water in the Step2 is 1:1:5.
6. The preparation method of a Ni-containing CuS/C composite material according to
claim 1, wherein the vulcanization-carbonization temperature in the Step 6 is 350
DEG C ~800 DEG C.
7. The preparation method of a Ni-containing CuS/C composite material according to
claim 1, wherein a purity of the powdered sulfur in the Step 6 is 99.95%.
8. The preparation method of a Ni-containing CuS/C composite material according to
claim 1, wherein in the Step 6, the way that the activated precursor and the powdered
sulfur are mixed in the high energy ball-grinding mill is, taking zirconia balls with a
particle size of 5mm and a particle size of lcm as a grinding media, and taking the
activated precursor and the powdered sulfur at a mass ratio of 1:1 as materials, then
grinding the grinding media and the materials at a mass ratio of 20:1 under the
protection of argon, at a speed of 300-500r/min, for 2h to obtain the mixed precursor.
9. The preparation method of a Ni-containing CuS/C composite material according to
claim 8, wherein under the protection of argon, the mixed precursor is obtained after a
two-hour grinding process at a speed of 500r/min.
10. An application of the Ni-containing CuS/C composite material obtained according
to the preparation method according to any of claims 1-9 to a positive electrode
material of a lithium-sulfur battery.
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| CN115010191A (en) * | 2022-07-05 | 2022-09-06 | 浙江帕瓦新能源股份有限公司 | Battery material precursor and preparation method and application thereof |
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| CN111883756B (en) * | 2020-07-23 | 2021-09-07 | 昆明理工大学 | Preparation method and application of Ni-containing CuS/C composite material |
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