CN113745530A - High-performance spherical phosphorus-doped nickel oxide lithium carbon dioxide battery positive electrode catalytic material and preparation method thereof - Google Patents
High-performance spherical phosphorus-doped nickel oxide lithium carbon dioxide battery positive electrode catalytic material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 34
- -1 nickel oxide lithium carbon dioxide Chemical compound 0.000 title claims abstract description 27
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 98
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 98
- WFLRGOXPLOZUMC-UHFFFAOYSA-N [Li].O=C=O Chemical compound [Li].O=C=O WFLRGOXPLOZUMC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000002243 precursor Substances 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000007790 solid phase Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 11
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 10
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
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- 238000001354 calcination Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000003017 phosphorus Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 2
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- 239000000243 solution Substances 0.000 description 25
- 229910052573 porcelain Inorganic materials 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 7
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- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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- 238000002485 combustion reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
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- 239000011574 phosphorus Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-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
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 239000011259 mixed solution Substances 0.000 description 1
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- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 230000004083 survival effect Effects 0.000 description 1
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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
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- 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
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Abstract
本发明属于电化学和新能源领域，涉及一种高性能球花状磷掺杂氧化镍锂二氧化碳电池正极催化材料及其制备方法。本发明制备材料为大小均一的磷掺杂氧化镍球花，球花的平均直径约为6微米，具有较大的比表面积(约235m2g‑1)，可用于锂二氧化碳电池的正极催化材料，可以得到很高的比容量和优异的循环稳定性，同时制备方法简便，仅通过简单水热反应和后续热处理即可获得，极具工业化生产价值和实际应用价值。
The invention belongs to the fields of electrochemistry and new energy, and relates to a high-performance spherical phosphorous doped nickel oxide lithium carbon dioxide battery cathode catalytic material and a preparation method thereof. The preparation material of the invention is phosphorus-doped nickel oxide balls with uniform size, the average diameter of the balls is about 6 microns, and the balls have a relatively large specific surface area (about 235m 2 g -1 ), which can be used as a positive electrode catalytic material for lithium carbon dioxide batteries , high specific capacity and excellent cycle stability can be obtained, and the preparation method is simple and can be obtained only by simple hydrothermal reaction and subsequent heat treatment, which has great industrial production value and practical application value.
Description
Technical Field
The invention belongs to the field of electrochemistry and new energy, and particularly relates to a preparation method of a spherical phosphorus-doped nickel oxide lithium carbon dioxide battery anode catalytic material, and application of an electrode material prepared by the method in a lithium carbon dioxide battery anode material.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Global warming has become a serious problem threatening human survival, carbon dioxide is regarded as a second greenhouse gas and has a high emission value, and the conventional carbon dioxide capture (post-combustion capture, pre-combustion capture and oxygen combustion) and sequestration lead to the generation of products such as carbon monoxide, methane, ethylene and the like, and the storage and conversion of the products further lead to energy consumption and environmental pollution. Lithium carbon dioxide batteries are known for their relatively high discharge potential (-2.8V) and theoretical specific capacity density (1876Wh kg)-1) Has good prospect in the fields of carbon dioxide fixation and energy storage. However, the intermediate product lithium carbonate is stable and difficult to decompose at low pressure, which can delay the reaction kinetics of the lithium-carbon dioxide battery, resulting in the lithium-carbon dioxide battery having too high an overpotential and low coulombic efficiency during the charging process. In order to improve the battery performance, it is necessary to develop a positive electrode catalytic material of a high-efficiency lithium carbon dioxide battery.
Researchers have made many efforts to find high-performance catalytic materials, among which noble metal and carbon-based materials have been widely studied, but the noble metal materials are expensive and the carbon-based materials cannot effectively decompose lithium carbonate, thus being limited in large-scale application. Transition metal oxides such as cobalt oxide, manganese oxide, nickel oxide, molybdenum oxide, and the like attract the attention of researchers due to their good catalytic performance and low price. Nickel oxide has been reported to decompose lithium carbonate efficiently at low potentials, but due to poor conductivity, nickel oxide is limited to catalyze the conversion of carbon dioxide in lithium carbon dioxide batteries.
Research shows that the nickel oxide material applied to the lithium-carbon dioxide anode catalyst can remarkably improve the cycle and rate performance of the lithium-carbon dioxide battery. If researchers synthesize nitrogen, sulfur and cobalt co-doped graphite nickel oxide composite nano particles by a hydrothermal method and an adsorption method, the nano particles are used as a positive electrode catalytic material of a lithium-carbon dioxide battery, and the current density is 100mA g-1Then, the discharge capacity can reach 13400mAh g-1(ii) a At a current density of 100mA g-1The specific cut-off capacity is 500mAh g-1The cycle life of the battery can reach 50 cycles. According to the research, the surface modification is carried out through defect engineering, oxygen vacancies are introduced into nickel oxide growing on carbon paper, and the electrode can stably circulate for 58 circles under the test condition of the cut-off voltage of 2.3-4.5V.
Although some progress has been made on the application of nickel oxide materials to the anode catalytic materials of lithium-carbon dioxide batteries at present, the related preparation methods reported at present are complex and involve carbon loading, polyatomic doping and the like, and are not beneficial to large-scale application.
Disclosure of Invention
Aiming at the defects of the technology, the invention provides a high-performance spherical phosphorus-doped nickel oxide lithium carbon dioxide battery anode catalytic material and a preparation method thereof. Meanwhile, the raw materials are easy to obtain and low in price, the preparation method is simple, and the lithium-carbon dioxide battery can be obtained only through hydrothermal reaction and subsequent heat treatment, so that the lithium-carbon dioxide battery provides effective benefits for large-scale industrial production and practical application of the lithium-carbon dioxide battery.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a high-performance spherical phosphorus-doped nickel oxide lithium carbon dioxide battery anode catalytic material, which comprises the following steps:
dissolving nickel salt and urea in an alcohol solution, and carrying out hydrothermal reaction to obtain a solid-phase precursor;
calcining the solid-phase precursor to obtain a nickel oxide spherical flower material;
and carrying out phosphating treatment on the nickel oxide spherical flower material to obtain the spherical flower-shaped phosphorus-doped nickel oxide material.
The invention provides a high-performance nickel oxide material which is cheap in raw materials and simple and convenient to prepare, and researches show that: compared with the existing hollow nickel phosphide material, the nickel oxide spherical phosphorus doped nickel oxide material prepared by carrying out phosphating treatment on the nickel oxide spherical material formed after calcination has special appearance, large specific surface area, good capacity performance and cycle performance, and can be used for lithium carbon dioxide batteries.
The second aspect of the invention provides the high-performance spherical phosphorus-doped nickel oxide lithium carbon dioxide battery anode catalytic material prepared by the method, wherein the structure of the hole in the spherical phosphorus-doped nickel oxide lithium carbon dioxide battery anode catalytic material is nano-scale, the pore diameter ranges from 7 nm to 15 nm, and the diameter of the spherical flower ranges from 5 microns to 7 microns.
In a third aspect of the invention, the application of the flower-like phosphorus-doped nickel oxide lithium carbon dioxide battery anode catalytic material in the preparation of a lithium carbon dioxide battery is provided.
The invention has the beneficial effects that:
(1) the spherical phosphorus-doped nickel oxide material is prepared by regulating the hydrothermal condition and the heat treatment condition, and is environment-friendly and low in production cost. It should be noted that the content of doped phosphorus affects the catalytic performance of the material as a catalytic material;
(2) the electrode material prepared by the invention has larger specific surface area (about 235 m)2g-1) Is beneficial to the mass transfer process and endows the material with good catalytic performance.
(3) The electrode anode catalytic material prepared by the invention has good morphology and electrochemical performance and can be used for preparing cathode catalytic materialsRenaturation and excellent cycle stability. In one embodiment of the invention, the electrode material is used at a current density of 100mA g-1The specific capacity of the first circle of charge and discharge reaches 13215/11660mAh g-1(ii) a At a current density of 200mA g-1The cut-off specific capacity is 600mAh g-1The cycle life of the battery can reach 70 times by charging and discharging under the test condition.
(4) The operation method is simple, low in cost, universal and easy for large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows the XRD test results of the spherical phosphorus-doped nickel oxide material synthesized in example 1;
FIG. 2 is a FESEM image of a spherical phosphorus-doped nickel oxide material synthesized in example 1;
FIG. 3 is a nitrogen adsorption-desorption isotherm and pore size distribution diagram of the spherical phosphorus-doped nickel oxide material synthesized in example 1;
FIG. 4 is the first charge-discharge diagram of the ball-flower-shaped phosphorus-doped nickel oxide material synthesized in example 1 when used in the test of a lithium-carbon dioxide battery under the test condition of a current density of 100mA g-1The cut-off voltage is 2.3-4.5V;
FIG. 5 is a graph of the cycle performance of the ball-flower-shaped phosphorus-doped nickel oxide material synthesized in example 1 when the material is used in a lithium-carbon dioxide battery test under the condition that the current density is 200mA g-1The specific cut-off capacity is 600mAh g-1。
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In one embodiment of the present invention, a method for preparing a spherical phosphorus-doped nickel oxide material is provided, which comprises the following steps:
s1, preparing a reaction solution: dissolving nickel nitrate hexahydrate and urea in ethanol to obtain a reaction solution;
s2, preparing a solid-phase precursor: s1, reacting the prepared reaction solution at the temperature of 120-150 ℃ for 6-9h, and purifying to obtain a solid-phase precursor after the reaction is finished;
s3, preparing a nickel oxide spherical flower material: s2, placing the prepared solid-phase precursor in a temperature of 200 ℃ and 300 ℃ for calcining for 2h, and obtaining the nickel oxide spherical flower material after the reaction is finished;
s4, preparing a spherical phosphorus-doped nickel oxide material: s3, calcining the prepared nickel oxide spherical material and sodium hypophosphite for 1-2h at 200-300 ℃, and obtaining a spherical phosphorus-doped nickel oxide material after the reaction is finished;
in another embodiment of the present invention, in step s1. the molar ratio of nickel nitrate hexahydrate/nickel chloride hexahydrate and urea is 1:1-1.5, and further, the molar ratio of nickel nitrate hexahydrate and urea is 1: 1;
in another embodiment of the present invention, in the step s2, the purification step includes separation, cleaning and drying, and further, the purification step includes centrifuging after the reaction is finished to obtain a sample, repeatedly washing the sample with water and an alcohol solvent, and drying to obtain a solid phase precursor;
in another embodiment of the present invention, in the step S3, the solid phase precursor is heat-treated in an air atmosphere, and the temperature rise rate is controlled to be 5 ℃ for min-1Calcining at 200-300 ℃ for 2 h;
in another specific embodiment of the present invention, in the step s4, the nickel oxide spherical flower material obtained in the step s3 is subjected to phosphating treatment in an argon atmosphere, and a mass ratio of sodium hypophosphite/phosphorus pentoxide to nickel oxide is 0.5-2: 1, controlling the heating rate to be 5 ℃ for min-1Calcining at 300 ℃ for 1-2 h;
in another embodiment of the present invention, a method for preparing a spherical phosphorus-doped nickel oxide material is provided, which comprises the following steps:
s1, preparing a reaction solution: mixing a mixture of 1: dissolving nickel nitrate hexahydrate and urea of 1 in ethanol and stirring to obtain a reaction solution;
s2, preparing a solid-phase precursor: s1, reacting the prepared reaction solution at the temperature of 120-150 ℃ for 6-9h, and purifying to obtain a solid-phase precursor after the reaction is finished;
s3, preparing a nickel oxide spherical flower material: s2, carrying out heat treatment on the prepared solid-phase precursor, and carrying out heat treatment at 5 ℃ for min in air atmosphere-1The temperature rise speed is kept at 200-300 ℃ for 2h, and the nickel oxide spherical flower material is obtained after the reaction is finished;
s4, preparing a spherical phosphorus-doped nickel oxide material: s3, calcining the prepared nickel oxide spherical flower material and sodium hypophosphite at 300 ℃ for 1-2h to obtain a spherical phosphorus-doped nickel oxide material after the reaction is finished;
in some embodiments, in the phosphating process, the nickel oxide spherulites and the phosphorus salt are respectively placed in two porcelain boats and calcined in the same tube furnace to obtain the high-performance spherulitic phosphorus doped nickel oxide material, the nickel oxide spherulites and the phosphorus salt do not need to be mixed, and the preparation method is simpler.
(1) In another embodiment of the present invention, there is provided a spherical phosphorus-doped nickel oxide material prepared by the above method, wherein the pores in the spherical phosphorus-doped nickel oxide material have a nano-scale structure, the pore diameters are mainly distributed between 7 nm and 15 nm, the pore diameters are concentrated around 11 nm, the appearance and the morphology of the spherical phosphorus-doped nickel oxide material are unique and uniform, and the diameter of the spherical flower is about 6 μm; the surface morphology leads the material to have larger specific surface area, is beneficial to the mass transfer process and endows the material with good catalytic performance.
In another embodiment of the present invention, a lithium-carbon dioxide battery positive electrode catalytic material is provided, wherein the lithium-carbon dioxide battery positive electrode catalytic material comprises the above-mentioned spherical phosphorus-doped nickel oxide material;
in another embodiment of the present invention, a lithium-carbon dioxide battery is provided, which comprises the above-mentioned cathode catalytic material and/or the above-mentioned spherical phosphorus-doped nickel oxide material.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1
The spherical phosphorus-doped nickel oxide material is prepared by the following steps:
(1) preparation of the reaction solution
Dissolving 1mmol of nickel nitrate hexahydrate and 1mmol of urea in 40mL of ethanol, and stirring for 1h to form a light green mixed solution;
(2) preparation of solid phase precursor
Transferring the solution prepared in the step (1) into a polytetrafluoroethylene inner container of 80mL, carrying out high-temperature high-pressure hydrothermal reaction, controlling the reaction temperature at 120 ℃ and the reaction time at 6h, cooling to room temperature after full reaction, carrying out centrifugal washing on the reaction product by deionized water and ethanol, and drying in the air at 60 ℃ for 12h to obtain a solid-phase precursor;
(3) preparation of nickel oxide materials
Putting the precursor collected in the step (2) into a muffle furnace, and carrying out air atmosphere at 5 ℃ for min-1The temperature is raised to 300 ℃ at the temperature raising speed, the temperature is kept for 2h, and when the muffle furnace is cooled to the room temperature, the obtained black sample is the nickel oxide material;
(4) preparation of spherical phosphorus-doped nickel oxide material
Putting the nickel oxide material and sodium hypophosphite collected in the step (3) into two porcelain boats respectively, and putting the porcelain boats and the nickel oxide material in the same tube furnace in an argon atmosphere at the temperature of 5 ℃ for min-1The temperature is raised to 300 ℃ at the temperature raising speed, the temperature is kept for 1h, and the obtained sample is the spherical phosphorus-doped nickel oxide material after the tubular furnace is cooled to the room temperature.
FIG. 1 shows the XRD test result of the spherical phosphorus-doped nickel oxide material synthesized by the method of the present invention, wherein the diffraction data is consistent with the face-centered cubic phase nickel oxide standard card (JCPDF 71-1179) and no other impurity phase appears, which indicates that the product is a high-purity phosphorus-doped nickel oxide material and no other impurity exists. FIG. 2 is a FESEM picture of a sample of spherical phosphorus-doped nickel oxide, and it can be seen from FIG. 2 that the surface morphology synthesized by the method of the present invention is spherical, and the diameter of the spherical is about 6 microns. FIG. 3 is a nitrogen adsorption-desorption isotherm and a pore size distribution diagram of the spherical phosphorus-doped nickel oxide material synthesized by the method of the present invention, showing that the pore size is mainly distributed between 7-15 nm, and is concentrated around 11 nm.
The electrode was made from the spherical phosphorus-doped nickel oxide material obtained in example 1 and tested for lithium carbon dioxide cell performance as follows: and (3) adding the following components in percentage by weight of 4: 4: 2, respectively weighing the spherical phosphorus-doped nickel oxide material, the carbon black and the polytetrafluoroethylene, mixing the materials with a certain volume of isopropanol, carrying out ultrasonic treatment for 30min to obtain catalyst slurry, uniformly dropwise adding the catalyst slurry on carbon paper to prepare a pole piece, and carrying out vacuum drying for 6h at 120 ℃. A metal lithium sheet is used as a negative electrode, and the electrolyte is 1mol L-1The lithium bis (trifluoromethanesulfonyl) imide/triethylene glycol dimethyl ether is assembled into the lithium-carbon dioxide battery by selecting a glass fiber diaphragm. All cells were assembled in an argon-filled glove box and then placed in a clean room with high purity carbon dioxide for constant current discharge/charge testing of lithium carbon dioxide cells on a LAND CT 2001A multichannel cell tester at room temperature.
FIG. 4 shows the current density of the assembled battery at 100mA g-1The first circle of charge and discharge performance. The electrode material of the invention is 100mA g-1Under the current density, the charging and discharging specific capacity reaches 13215/11660mAh g-1. FIG. 5 shows the assembled battery at a current density of 200mA g-1Cycling performance of the time. The specific cut-off capacity of the electrode material is 600mAh g-1The cycle life can reach 70 circles, and the cycle performance is excellent.
Example 2
The spherical phosphorus-doped nickel oxide material is prepared by the following steps:
(1) preparation of the reaction solution
Dissolving 1mmol of nickel nitrate hexahydrate and 1mmol of urea in 40mL of ethanol, and stirring for 1h to form a light green mixed-color solution;
(2) preparation of solid phase precursor
Transferring the solution prepared in the step (1) into a polytetrafluoroethylene inner container of 80mL, carrying out high-temperature high-pressure hydrothermal reaction, controlling the reaction temperature at 120 ℃ and the reaction time at 9h, cooling to room temperature after full reaction, carrying out centrifugal washing on the reaction product by deionized water and ethanol, and drying in the air at 60 ℃ for 12h to obtain a solid-phase precursor;
(3) preparation of nickel oxide materials
Putting the precursor collected in the step (2) into a muffle furnace, and carrying out air atmosphere at 5 ℃ for min-1The temperature is raised to 300 ℃ at the temperature raising speed, the temperature is kept for 2h, and when the muffle furnace is cooled to the room temperature, the obtained black sample is the nickel oxide material;
(4) preparation of spherical phosphorus-doped nickel oxide material
Putting the nickel oxide material and sodium hypophosphite collected in the step (3) into two porcelain boats respectively, and putting the porcelain boats and the nickel oxide material in the same tube furnace in an argon atmosphere at the temperature of 5 ℃ for min-1The temperature is raised to 300 ℃ at the temperature raising speed, the temperature is kept for 1h, and the obtained sample is the spherical phosphorus-doped nickel oxide material after the tubular furnace is cooled to the room temperature.
Example 3
The spherical phosphorus-doped nickel oxide material is prepared by the following steps:
(1) preparation of the reaction solution
Dissolving 1mmol of nickel nitrate hexahydrate and 1mmol of urea in 40mL of ethanol, and stirring for 1h to form a light green mixed-color solution;
(2) preparation of solid phase precursor
Transferring the solution prepared in the step (1) into a polytetrafluoroethylene inner container of 80mL, carrying out high-temperature high-pressure hydrothermal reaction, controlling the reaction temperature at 150 ℃ and the reaction time at 6h, cooling to room temperature after full reaction, carrying out centrifugal washing on the reaction product by deionized water and ethanol, and drying in the air at 60 ℃ for 12h to obtain a solid-phase precursor;
(3) preparation of nickel oxide materials
Putting the precursor collected in the step (2) into a muffle furnace, and carrying out air atmosphere at 5 ℃ for min-1The temperature is raised to 300 ℃ at the temperature raising speed, the temperature is kept for 2h, and when the muffle furnace is cooled to the room temperature, the obtained black sample is the nickel oxide material;
(4) preparation of spherical phosphorus-doped nickel oxide material
Nickel oxide collected in the step (3)The material and sodium hypophosphite are respectively placed in two porcelain boats, and are placed in the same tube furnace under the argon atmosphere for 5 ℃ min-1The temperature is raised to 300 ℃ at the temperature raising speed, the temperature is kept for 1h, and the obtained sample is the spherical phosphorus-doped nickel oxide material after the tubular furnace is cooled to the room temperature.
Example 4
The spherical phosphorus-doped nickel oxide material is prepared by the following steps:
(1) preparation of the reaction solution
Dissolving 1mmol of nickel nitrate hexahydrate and 1mmol of urea in 40mL of ethanol, and stirring for 1h to form a light green mixed-color solution;
(2) preparation of solid phase precursor
Transferring the solution prepared in the step (1) into a polytetrafluoroethylene inner container of 80mL, carrying out high-temperature high-pressure hydrothermal reaction, controlling the reaction temperature at 150 ℃ and the reaction time at 9h, cooling to room temperature after full reaction, carrying out centrifugal washing on the reaction product by deionized water and ethanol, and drying in the air at 60 ℃ for 12h to obtain a solid-phase precursor;
(3) preparation of nickel oxide materials
Putting the precursor collected in the step (2) into a muffle furnace, and carrying out air atmosphere at 5 ℃ for min-1The temperature is raised to 300 ℃ at the temperature raising speed, the temperature is kept for 2h, and when the muffle furnace is cooled to the room temperature, the obtained black sample is the nickel oxide material.
(4) Preparation of spherical phosphorus-doped nickel oxide material
Putting the nickel oxide material and sodium hypophosphite collected in the step (3) into two porcelain boats respectively, and putting the porcelain boats and the nickel oxide material in the same tube furnace in an argon atmosphere at the temperature of 5 ℃ for min-1The temperature is raised to 300 ℃ at the temperature raising speed, the temperature is kept for 1h, and the obtained sample is the spherical phosphorus-doped nickel oxide material after the tubular furnace is cooled to the room temperature.
Example 5
The spherical phosphorus-doped nickel oxide material is prepared by the following steps:
(1) preparation of the reaction solution
Dissolving 1mmol of nickel nitrate hexahydrate and 1mmol of urea in 40mL of ethanol, and stirring for 1h to form a light green mixed-color solution;
(2) preparation of solid phase precursor
Transferring the solution prepared in the step (1) into a polytetrafluoroethylene inner container of 80mL, carrying out high-temperature high-pressure hydrothermal reaction, controlling the reaction temperature at 120 ℃ and the reaction time at 6h, cooling to room temperature after full reaction, carrying out centrifugal washing on the reaction product by deionized water and ethanol, and drying in the air at 60 ℃ for 12h to obtain a solid-phase precursor;
(3) preparation of nickel oxide materials
Putting the precursor collected in the step (2) into a muffle furnace, and carrying out air atmosphere at 5 ℃ for min-1The temperature is raised to 300 ℃ at the temperature raising speed, the temperature is kept for 2h, and when the muffle furnace is cooled to the room temperature, the obtained black sample is the nickel oxide material;
(4) preparation of spherical phosphorus-doped nickel oxide material
Putting the nickel oxide material and sodium hypophosphite collected in the step (3) into two porcelain boats respectively, and putting the porcelain boats and the nickel oxide material in the same tube furnace in an argon atmosphere at the temperature of 5 ℃ for min-1The temperature is raised to 300 ℃ at the temperature raising speed, the temperature is kept for 1h, and the obtained sample is the spherical phosphorus-doped nickel oxide material after the tubular furnace is cooled to the room temperature.
Example 6
The spherical phosphorus-doped nickel oxide material is prepared by the following steps:
(1) preparation of the reaction solution
Dissolving 1mmol of nickel nitrate hexahydrate and 1mmol of urea in 40mL of ethanol, and stirring for 1h to form a light green mixed-color solution;
(2) preparation of solid phase precursor
Transferring the solution prepared in the step (1) into a polytetrafluoroethylene inner container of 80mL, carrying out high-temperature high-pressure hydrothermal reaction, controlling the reaction temperature at 120 ℃ and the reaction time at 6h, cooling to room temperature after full reaction, carrying out centrifugal washing on the reaction product by deionized water and ethanol, and drying in the air at 60 ℃ for 12h to obtain a solid-phase precursor;
(3) preparation of nickel oxide materials
Putting the precursor collected in the step (2) into a muffle furnace, and carrying out air atmosphere at 5 ℃ for min-1The temperature is raised to 300 ℃ at the temperature raising speed, the temperature is kept for 2h, and when the muffle furnace is cooled to the room temperature, the obtained black sample is the nickel oxide material;
(4) preparation of spherical phosphorus-doped nickel oxide material
Putting the nickel oxide material and sodium hypophosphite collected in the step (3) into two porcelain boats respectively, and putting the porcelain boats and the nickel oxide material in the same tube furnace in an argon atmosphere at the temperature of 5 ℃ for min-1The temperature is raised to 300 ℃ at the temperature raising speed, the temperature is kept for 2h, and the obtained sample is the spherical phosphorus-doped nickel oxide material after the tubular furnace is cooled to the room temperature.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
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