CN106532030A - Calcium molybdate lithium ion battery negative electrode material and preparation method thereof - Google Patents
Calcium molybdate lithium ion battery negative electrode material and preparation method thereof Download PDFInfo
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- CN106532030A CN106532030A CN201611230603.6A CN201611230603A CN106532030A CN 106532030 A CN106532030 A CN 106532030A CN 201611230603 A CN201611230603 A CN 201611230603A CN 106532030 A CN106532030 A CN 106532030A
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- Prior art keywords
- lithium ion
- ion battery
- battery negative
- calcium molybdate
- preparation
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Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 120
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 117
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000007773 negative electrode material Substances 0.000 title abstract description 7
- 239000000376 reactant Substances 0.000 claims abstract description 60
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 58
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 235000010489 acacia gum Nutrition 0.000 claims abstract description 37
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 34
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 34
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 34
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 89
- 239000011159 matrix material Substances 0.000 claims description 63
- 239000011148 porous material Substances 0.000 claims description 57
- 229920000084 Gum arabic Polymers 0.000 claims description 36
- 239000000205 acacia gum Substances 0.000 claims description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 14
- 229910052791 calcium Inorganic materials 0.000 claims description 14
- 239000010406 cathode material Substances 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 241000978776 Senegalia senegal Species 0.000 claims 3
- 244000171897 Acacia nilotica subsp nilotica Species 0.000 claims 2
- PMUIBVMKQVKHBE-UHFFFAOYSA-N [S].NC(N)=O Chemical compound [S].NC(N)=O PMUIBVMKQVKHBE-UHFFFAOYSA-N 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract 1
- 239000001785 acacia senegal l. willd gum Substances 0.000 abstract 1
- 244000215068 Acacia senegal Species 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 238000003860 storage Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 6
- 229920001206 natural gum Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 159000000007 calcium salts Chemical class 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 150000004676 glycans Chemical class 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229920001282 polysaccharide Polymers 0.000 description 4
- 239000005017 polysaccharide Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- USOPFYZPGZGBEB-UHFFFAOYSA-N calcium lithium Chemical compound [Li].[Ca] USOPFYZPGZGBEB-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000411 inducer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- AEMOLEFTQBMNLQ-AQKNRBDQSA-N D-glucopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-AQKNRBDQSA-N 0.000 description 1
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MOOYSSSIVSFZQA-UHFFFAOYSA-N [Li].[Mo] Chemical compound [Li].[Mo] MOOYSSSIVSFZQA-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- SRBFZHDQGSBBOR-QMKXCQHVSA-N alpha-L-arabinopyranose Chemical compound O[C@H]1CO[C@@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-QMKXCQHVSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002969 artificial stone Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- FFYADPKAFBYAMU-UHFFFAOYSA-N ethane-1,2-diol;urea Chemical compound NC(N)=O.OCCO FFYADPKAFBYAMU-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940097043 glucuronic acid Drugs 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a calcium molybdate lithium ion battery negative electrode material and a preparation method thereof. The preparation method comprises the steps of: sequentially adding preset mass of arabic gum, ammonium molybdate and thiourea into mixed solution of water and ethylene glycol, and sufficiently stirring to obtain target solution; in a preset temperature range and preset time, performing a hydrothermal reaction on the target solution to obtain a first reactant; and carrying out washing, drying and high-temperature calcination on the first reactant to obtain the symmetric concave macroporous spherical micron calcium molybdate lithium ion battery negative electrode material. By the preparation method, the micron-level calcium molybdate lithium ion battery negative electrode material with a symmetric concave macroporous spherical microstructure can be obtained, has a large specific surface area, and is uniform and complete in spherical structure and good in consistency of size, so that stability of a negative electrode of a lithium ion battery prepared by adopting the calcium molybdate lithium ion battery negative electrode is well improved.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of calcium molybdate lithium ion battery negative material and
Its preparation method.
Background technology
Since coming out from eighties of last century lithium ion battery at the beginning of the nineties, with graphitized carbon material as negative pole, cobalt acid lithium material
Lithium ion battery technology for positive pole has obtained huge development.Lithium ion battery is due to output voltage height, energy density
The advantages of high, little environmental pollution and memory-less effect, it is widely used in the fields such as various portable sets and electric automobile.
However, as the portable set with mobile phone, notebook computer etc. as representative is constantly to miniaturization, intellectuality
And lightening direction is developed, and electric automobile to aspects such as the energy density of motive-power battery, security and costs more and more
High requirement, the performance of conventional lithium ion battery cannot gradually meet the demand of above-mentioned development, and wherein lithium ion battery is negative
Pole material is one of important restraining factors.Wherein, the subject matter that traditional graphite cathode material is present is：(1) artificial stone
Ink need to be processed in 1900 DEG C～2800 DEG C Jing high temperature graphitizations and is obtained, and preparation temperature is high；(2) graphite cathode material theory specific volume
Amount is only 372mAh/g, cannot gradually meet the fields such as various portable sets and electric automobile to lithium ion battery higher-energy
The demand of density；(3) negative pole structure of the lithium ion battery with graphitized carbon material as negative pole is fragile, and security is poor.
Thus, the performance of the negative material of lithium ion battery how is improved, becomes the focus that people are devoted to studying always
And Important Problems.
The content of the invention
Based on this, it is necessary to for traditional graphite negative material of lithium ion battery specific capacity is relatively low, security is poor and
A kind of larger technical problem of preparation technology difficulty, there is provided calcium molybdate lithium ion battery negative material and preparation method thereof, it is described
Calcium molybdate lithium ion battery negative material has the microstructure of symmetrical matrix pore sphere, and specific capacity is higher, and security is preferable,
Electro-chemical activity is high, good cycle, prepares with excellent storage lithium performance and easily.
A kind of preparation method of calcium molybdate lithium ion battery negative material, comprises the steps：To the mixed of water and ethylene glycol
Gum arabic, ammonium molybdate and the thiocarbamide of preset quality are sequentially added in closing solution, is sufficiently stirred for, obtain target solution；Pre-
If in temperature range and Preset Time, hydro-thermal reaction is carried out to the target solution, the first reactant is obtained；It is anti-to described first
Answer thing to carry out washing, be dried and high-temperature calcination, obtain symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material；
Wherein, the calcium content of the gum arabic is 0.02%～2%.
Wherein in one embodiment, sequentially add in the mixed solution to water and ethylene glycol preset quality I
Uncle's natural gum, ammonium molybdate and thiocarbamide, are sufficiently stirred for, and obtain target solution, comprise the steps：
The gum arabic of the first mass is added in the mixed solution of water and ethylene glycol, is sufficiently stirred for obtaining the first reaction
Liquid；The ammonium molybdate of the second mass is added in first reactant liquor, is stirred to the ammonium molybdate and is completely dissolved that to obtain second anti-
Answer liquid；The thiocarbamide of the 3rd mass is added in second reactant liquor, is stirred to the thiocarbamide to be completely dissolved and is obtained the target
Solution.
Wherein in one embodiment, in the mixed solution, the volume ratio of water and ethylene glycol is 1: (0.9～1.2).
Wherein in one embodiment, the mass ratio 1 of the gum arabic and the mixed solution: (5～150).
Wherein in one embodiment, the ammonium molybdate is 1 with the mass ratio of the gum arabic: (1.3～2.1).
Wherein in one embodiment, the thiocarbamide is 1 with the mass ratio of the ammonium molybdate: (0.9～6.1).
Wherein in one embodiment, the preset temperature range is 150 DEG C～200 DEG C, and the Preset Time is 30min
～360min.
Wherein in one embodiment, the mode of the drying is to adopt constant temperature drying.
Wherein in one embodiment, the temperature of the high-temperature calcination is 500 DEG C～700 DEG C.
Wherein in one embodiment, the calcium molybdate lithium ion battery negative material is by institute in above-mentioned any one embodiment
The preparation method for stating calcium molybdate lithium ion battery negative material is prepared.
Above-mentioned calcium molybdate lithium ion battery negative material and preparation method thereof, obtains micro- with symmetrical matrix pore sphere
Structure micron order calcium molybdate lithium ion battery negative material is seen, with larger specific surface area, electricity in lithium ion battery is increased
Solution liquid and the contact area of electrode material, improve the effect of impregnation of electrolyte, so as to shorten the transmission of lithium ion and electronics
Path so that the embedded and abjection of lithium ion more fully, and then causes the specific capacity of lithium ion battery higher, electro-chemical activity
Height, good reversibility, good cycle, with excellent storage lithium performance, and chondritic is uniformly complete, the uniformity of size compared with
It is good so that the negative pole stability of the lithium ion battery prepared using calcium molybdate lithium ion battery negative material has obtained carrying well
It is high.Additionally, the preparation method of above-mentioned calcium molybdate lithium ion battery negative material, process is simple is workable, favorable reproducibility,
It is and raw material sources are extensively, cheap, preferably reduce production cost.
Description of the drawings
Fig. 1 is the schematic flow sheet of the preparation method of the calcium molybdate lithium ion battery negative material of an embodiment；
Fig. 2 is the schematic flow sheet of the preparation method of the S110 of another embodiment；
Fig. 3 is the ESEM of the symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material of an embodiment
Figure；
Fig. 4 is the projection Electronic Speculum of the symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material of an embodiment
Figure；
Fig. 5 is the XRD spectrum of the symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material of an embodiment；
Fig. 6 is the XPS collection of illustrative plates of the symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material of an embodiment；
Fig. 7 is the symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material of an embodiment in 0.01-
The 1st, 2,50 charging and discharging curve figures under 3.0V voltages, under 200mAh/g current densities；
Fig. 8 is the symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material of an embodiment in 0.01-
Circulation volume and its coulombic efficiency curve map under 3.0V voltages, under 200mAh/g current densities；
Fig. 9 is the symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material of another embodiment in 0.01-
Circulation volume and its coulombic efficiency curve map under 3.0V voltages, under 200mAh/g current densities；
Figure 10 is the symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material of an embodiment in 0.01-
Under 3.0V voltages, current density is respectively the high rate performance under 50mA/g, 100mA/g, 200mA/g, 400mA/g, 200mA/g and surveys
Attempt.
Specific embodiment
It is understandable to enable the above objects, features and advantages of the present invention to become apparent from, below in conjunction with the accompanying drawings to the present invention
Specific embodiment be described in detail.Elaborate many details in order to fully understand this in the following description
It is bright.But the present invention can be implemented with being much different from alternate manner described here, and those skilled in the art can be not
Similar improvement is done in the case of running counter to intension of the present invention, therefore the present invention is not limited by following public specific embodiment.
In describing the invention, it is to be understood that term " first ", " second " are only used for describing purpose, and can not
It is interpreted as indicating or implying relative importance or the implicit quantity for indicating indicated technical characteristic.Thus, define " the
One ", at least one this feature can be expressed or be implicitly included to the feature of " second ".In describing the invention, " multiple "
It is meant that at least two, such as two, three etc., unless otherwise expressly limited specifically.
The preparation method of calcium molybdate lithium ion battery negative material according to embodiments of the present invention is described below in conjunction with the accompanying drawings.
It should be noted that main body of the negative material of lithium ion battery primarily as storage lithium, in charge and discharge process
Realize the embedded of lithium ion and deviate from.The specific capacity of traditional calcium molybdate is higher than graphite, in the process of lithium ion battery discharge and recharge
Middle Stability Analysis of Structures.However, as the electric conductivity of material itself is poor, being unfavorable for that electronics is negative in traditional calcium molybdate lithium ion battery
Spread in the material of pole, it is impossible to preferably realize the embedded of lithium ion and deviate from.
In order to solve the above problems, as shown in figure 1, the preparation side of the calcium molybdate lithium ion battery negative material of an embodiment
Method comprises the steps：
S110：Gum arabic, ammonium molybdate and the sulphur of preset quality are sequentially added in the mixed solution of water and ethylene glycol
Urea, is sufficiently stirred for, and obtains target solution liquid.
For example, S110 specifically includes following steps：
S111：The gum arabic of the first mass is added in the mixed solution of water and ethylene glycol, is sufficiently stirred for obtaining
One reactant liquor.For example, mixing time is 20min～60min.
S112：The ammonium molybdate of the second mass is added in the first reactant liquor, is stirred to ammonium molybdate to be completely dissolved and is obtained second
Reactant liquor.For example, mixing time is 20min～60min.
S113：The thiocarbamide of the 3rd mass is added in the second reactant liquor, is stirred to thiocarbamide to be completely dissolved and is obtained target solution.
Wherein, target solution is brown yellow transparent liquid.For example, mixing time is 30min～90min.
For example, it is stirred under conditions of mechanical agitation so that gum arabic, ammonium molybdate and the thiocarbamide for sequentially adding
It is completely dissolved, obtains target solution.
In order that symmetrical matrix pore sphere micron calcium molybdate in subsequent reactions, is obtained in that, and in the present embodiment, choosing
With gum arabic as calcium source.Relative to calcium salts such as calcium chloride, calcium nitrate, gum arabic can not only provide calcium source, more
Importantly, gum arabic as structure inducer, can promote the calcium molybdate of the spherical special construction of symmetrical matrix macropore
Formation, this is that the calcium salts such as traditional calcium chloride, calcium nitrate cannot be realized.
In order that the ball calcium molybdate obtained in subsequent reactions has symmetrical concave structure, in the present embodiment, select
Source of the ammonium molybdate as molybdenum acid ion.Relative to other molybdates, such as sodium molybdate and potassium molybdate etc., by reactant
Ammonium molybdate is added in system so that the spherical calcium molybdate obtained in subsequent reactions has symmetrical concave structure, and this is to adopt sodium molybdate
Or other molybdates such as potassium molybdate cannot be realized as molybdenum acid ion.
In order that the chondritic of the symmetrical matrix pore sphere micron calcium molybdate obtained in subsequent reactions is more uniform
The uniformity of complete and size preferably, in the present embodiment, adds thiocarbamide in reaction system, so, thiocarbamide by with I
Uncle's natural gum, molybdate and mixed solution each component compounding, form special solution environmental, obtain in enabling to subsequent reactions
The chondritic of symmetrical matrix pore sphere micron calcium molybdate is more uniform and complete.
S120：In preset temperature range and Preset Time, hydro-thermal reaction is carried out to the target solution, obtain first anti-
Answer thing.
For example, target solution is proceeded in reactor, in preset temperature range and Preset Time, carries out hydro-thermal reaction.
Hydro-thermal reaction is referred in closed reaction vessel, with the fluid such as the aqueous solution or steam as medium, high by heating creation one
The reaction carried out by warm reaction under high pressure environment.And for example, reactor is polytetrafluoroethyllining lining reactor, due in polytetrafluoroethylene (PTFE)
The characteristics of lining reactor has antiacid alkali resistant and resists various organic solvents, and high temperature resistant, coefficient of friction are extremely low, preferably avoid
The generation of side reaction in hydro-thermal reaction, and beneficial to the taking-up of follow-up symmetrical matrix pore sphere micron molybdic acid calcium product.And for example, instead
The volume for answering kettle is 100ml～200ml.
For example, preset temperature range is 150 DEG C～200 DEG C.And for example, preset temperature range is 160 DEG C～180 DEG C.And for example,
Preset temperature range is 170 DEG C～195 DEG C.And for example, preset temperature range is 178 DEG C.And for example, Preset Time be 30min～
360min.And for example, Preset Time is 40min～230min.And for example, Preset Time is 130min～350min.And for example, when presetting
Between be 200min.One embodiment is, when preset temperature range is located at 150 DEG C～200 DEG C, Preset Time be 30min～
During 360min, symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material is obtained in that.
S130：First reactant is carried out washing, is dried and high-temperature calcination, symmetrical matrix pore sphere micron is obtained
Calcium molybdate lithium ion battery negative material.
For example, first reactant is carried out successively washing, is dried and high-temperature calcination, obtain symmetrical matrix pore sphere
Micron calcium molybdate lithium ion battery negative material.In order that the first reactant is purer, for example, the first reactant is carried out
Wash for several times.And for example, the first reactant is washed for several times using deionized water and alcohol.So so that the first reactant
In unreacted reagent thoroughly removed so that the first reactant is purer.For example, adopt quality for the first reactant 5～
100 times of deionized water carries out first time washing, and quality is adopted after filtration for the alcohol of 5～20 times of the first reactant carries out second
Secondary washing, adopting quality after filtration again for the deionized water of 5～10 times of the first reactant carries out third time washing, so, favorably
More uniform and complete symmetrical matrix pore sphere micron calcium molybdate, i.e. calcium molybdate microballoon are obtained in subsequent step, also known as
Calcium molybdate microparticle, can serve as negative material.
In order that the first reactant after washing is thoroughly dried, for example, dry mode is to adopt constant temperature drying.
For example, by washing after the first reactant filter after be dried；For example, the drying includes drying or dries；And for example, will
First reactant carries out constant temperature drying in proceeding to drying box.And for example, the temperature of drying is 50 DEG C～80 DEG C.And for example, the temperature of drying
Spend for 55 DEG C～70 DEG C.And for example, the temperature of drying is 65 DEG C～74 DEG C.And for example, the time of drying is 12h～24h.And for example, dry
The dry time is 13h～19h.And for example, the time of drying is 16h～22h.And for example, the time of drying is 18h.So so that Jing
The first reactant crossed after washing is thoroughly dried, and is conducive to the high-temperature calcination of subsequent step.
In order to remove the organic impurities in the first reactant, meanwhile, the crystal property of the first reactant is improved, so as to obtain
Chondritic with symmetrical matrix pore sphere micron calcium molybdate, is being washed to first reactant and is being dried it
Afterwards, high-temperature calcination is carried out to dried first reactant.For example, the temperature of high-temperature calcination is 500 DEG C～700 DEG C.And for example, it is high
The temperature of temperature calcining is 550 DEG C～650 DEG C.And for example, the temperature of high-temperature calcination is 600 DEG C～690 DEG C.And for example, high-temperature calcination
Temperature is 650 DEG C.And for example, high temperature is carried out in the atmosphere furnace that dried first reactant is proceeded to nitrogen～hydrogen gas mixture
Calcining.And for example, atmosphere furnace with 1.0 DEG C/min～1.5 DEG C/min ramps to 650 DEG C.And for example, atmosphere furnace is first preheated to 300
DEG C～500 DEG C, dried first reactant is then placed in, then with 1.0 DEG C/min～1.5 DEG C/min ramps to 650
℃.And for example, atmosphere furnace with 1.1 DEG C/min～1.3 DEG C/min ramps to 690 DEG C.And for example, atmosphere furnace with 1.2 DEG C/min～
1.4 DEG C/min ramps are to 550 DEG C.And for example, atmosphere furnace with 1.0 DEG C/min ramps to 650 DEG C.So, on the one hand very
The organic impurities in the first reaction is eliminated well, on the other hand, it is possible to increase the crystal property of the first reactant, and then, energy
Enough to obtain the chondritic with symmetrical matrix pore sphere micron calcium molybdate and uniform complete, the uniformity of size is preferable.
By above-mentioned reaction, symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material, phase are obtained in that
For traditional calcium molybdate, the calcium molybdate lithium ion battery negative material obtained in the present embodiment has special symmetrical matrix big
The spherical microstructure in hole, with larger specific surface area, preferably increases electrolyte and electrode material in lithium ion battery
Contact area, improves the effect of impregnation of electrolyte, so as to shorten the transmission path of lithium ion and electronics so that lithium ion
It is embedded and deviate from more fully, and then so that the specific capacity of lithium ion battery is higher, and electro-chemical activity is high, good cycle,
With excellent storage lithium performance.Additionally, whole course of reaction, process is simple is workable, favorable reproducibility, and raw material sources
Extensively, it is cheap, preferably reduce preparation cost.
In another embodiment, in order that the follow-up gum arabic for adding, ammonium molybdate and thiocarbamide fully dissolve, and to obtain
The micron-sized calcium molybdate for obtaining symmetrical matrix pore sphere provides good solvent environment, for example, in S110, water in mixed solution
Volume ratio with ethylene glycol is 1: (0.9～1.2).And for example, in mixed solution, the volume ratio of water and ethylene glycol is 1: (0.9～1).
And for example, in mixed solution, the volume ratio of water and ethylene glycol is 1: (0.99～1.1).And for example, water and ethylene glycol in mixed solution
Volume ratio is 1: 1 or 1: 1.05.In such manner, it is possible to so that the follow-up gum arabic for adding, ammonium molybdate and thiocarbamide fully dissolve, and
Micron-sized calcium molybdate to obtain symmetrical matrix pore sphere provides good solvent environment.Wherein, it is purer in order to obtain
Calcium molybdate lithium ion battery negative material, for example, water is deionized water.
In another embodiment, in order to promote the formation of the calcium molybdate of the spherical special construction of symmetrical matrix macropore, for example, Ah
The main component of uncle's natural gum is drawn to include that macromolecule polysaccharide, the calcium salt of macromolecule polysaccharide, the magnesium salts of macromolecule polysaccharide and macromolecule are more
The sylvite of sugar.And for example, macromolecule polysaccharide is one or more in pectinose, galactolipin and glucuronic acid.And for example, I
The calcium content of uncle's natural gum is 0.02%～2%.And for example, the calcium content of gum arabic is 0.02%～1.2%.And for example, I
The calcium content of uncle's natural gum is 1%～1.9%.And for example, the calcium content of gum arabic is 1%.Thus it is possible, on the one hand, Arabic tree
Glue provides the calcium salt of calcium molybdate lithium ion battery negative material, and on the other hand, gum arabic can promote as structure inducer
Enter the formation of the calcium molybdate of the spherical special construction of symmetrical matrix macropore.
In another embodiment, in order to obtain symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material, and
Enable to the chondritic of symmetrical matrix pore sphere micron calcium molybdate more uniform and complete, for example, gum arabic with
The mass ratio of mixed solution is 1: (5～150).And for example, gum arabic and the mass ratio of mixed solution are 1: (10～90).Again
Such as, gum arabic and the mass ratio of mixed solution are 1: (80～130)；For example, the quality of gum arabic and mixed solution
Than for 1: 100.And for example, ammonium molybdate and the mass ratio of gum arabic are 1: (1.3～2.1).And for example, ammonium molybdate and Arabic tree
The mass ratio of glue is 1: (1.3～1.8).And for example, ammonium molybdate and the mass ratio of gum arabic are 1: (1.7～2)；For example, molybdenum
Sour ammonium is 1: 1.8 with the mass ratio of gum arabic.And for example, thiocarbamide and the mass ratio of ammonium molybdate are 1: (0.9～6.1).And for example,
Thiocarbamide is 1 with the mass ratio of ammonium molybdate: (1.9～4.1).And for example, thiocarbamide and the mass ratio of ammonium molybdate are 1: (3.9～5.1)；Example
Such as, thiocarbamide and the mass ratio of ammonium molybdate are 1: 4.For example, the quality of mixed solution is 50g～500g；And for example, the matter of mixed solution
Measure as 100g～200g；And for example, the quality of mixed solution is 120g；And for example, the quality of gum arabic be 1g～5g, i.e. Ah
The quality for drawing uncle's natural gum is 1g～5g, similarly hereinafter.And for example, the quality of gum arabic is 1.3g～4g.And for example, gum arabic
Quality is 3g～4g；For example, the quality of gum arabic is 3.5g.And for example, the quality of ammonium molybdate is 0.5g～2.5g.And for example,
The quality of ammonium molybdate is 1g～1.5g.And for example, the quality of ammonium molybdate is 1.4g～2.3g；For example, the quality of ammonium molybdate is 1.5g.
And for example, the quality of thiocarbamide is 0.4g～2.0g.And for example, the quality of thiocarbamide is 0.5g～1.0g.And for example, the quality of thiocarbamide is 0.9g
～1.8g；For example, the quality of thiocarbamide is 1.3g.By the mixed solution of water and ethylene glycol, gum arabic, ammonium sulfate and thiocarbamide
Compounding, form specific reaction system so that in follow-up hydro-thermal reaction, symmetrical matrix pore sphere micron can be obtained
Calcium molybdate lithium ion battery negative material, and it is more equal to enable to the chondritic of symmetrical matrix pore sphere micron calcium molybdate
It is even and complete.
The preparation method of above-mentioned calcium molybdate lithium ion battery negative material, obtains the microcosmic with symmetrical matrix pore sphere
Structure micron order calcium molybdate lithium ion battery negative material, with larger specific surface area, preferably increases lithium ion battery
The contact area of middle electrolyte and electrode material, improves the effect of impregnation of electrolyte, so as to shorten lithium ion and electronics
Transmission path so that the embedded and abjection of lithium ion is more abundant.Further so that the specific capacity of lithium ion battery is higher, electrification
Learn activity high, good reversibility, good cycle, with excellent storage lithium performance.
The preparation method of above-mentioned calcium molybdate lithium ion battery negative material, obtains the microcosmic with symmetrical matrix pore sphere
Structure micron order calcium molybdate, and chondritic is uniformly complete, the uniformity of size is preferable so that using calcium molybdate lithium ion battery
The negative pole stability of lithium ion battery prepared by negative material has obtained improving well, and then, it is possible to increase adopt calcium molybdate
The security of lithium ion battery prepared by lithium ion battery negative material.
The preparation method of above-mentioned calcium molybdate lithium ion battery negative material, process is simple are workable, favorable reproducibility,
It is and raw material sources are extensively, cheap, preferably reduce production cost.
On the basis of the preparation method of above-mentioned calcium molybdate lithium ion battery negative material, the present invention also provides a kind of molybdic acid
Calcium lithium ion battery negative material, the calcium molybdate lithium ion battery negative material are born by sour calcium described in any of the above-described embodiment
The preparation method of pole material is prepared, so as to calcium molybdate lithium ion battery negative material is with symmetrical matrix pore sphere
Microstructure, with larger specific surface area, preferably increase contact of the electrolyte with electrode material in lithium ion battery
Area, improves the effect of impregnation of electrolyte, shortens the transmission path of lithium ion and electronics so that lithium ion it is embedded and de-
Go out more abundant.Further so that had using lithium ion battery prepared by above-mentioned calcium molybdate lithium ion battery negative material higher
Specific capacity, preferable electro-chemical activity, preferable cycle performance, and with excellent storage lithium performance.
It is below specific embodiment, is specifically described the preparation method of calcium molybdate lithium ion battery negative material.
Embodiment 1
Carry out being sufficiently stirred for obtaining first during 1.0g gum arabics are added to 30mL water and 30mL ethylene glycol mixtures
Reactant liquor；In the first reactant liquor, the ammonium molybdate stirring 20min of addition 0.5g is completely dissolved to solid particle and obtains the second reaction
Liquid；The thiocarbamide of 0.3883g is added into the second reactant liquor to be sufficiently stirred for 30min and target solution is obtained to grain dissolution, then will
Target solution is transferred in 100mL teflon-lined reactors after 180 DEG C of high-temperature storage 6h, obtains the first reactant,
First reactant is brown ceramic powder.
The first reactant is cleaned using deionized water and absolute ethyl alcohol, by the first reactant for completing to clean 60
Constant temperature 12h in DEG C drying box, the first reactant for completing freeze-day with constant temperature is proceeded in the atmosphere furnace of nitrogen～hydrogen gas mixture,
Atmosphere furnace obtains symmetrical matrix pore sphere micron calcium molybdate lithium ion with 1 DEG C/min ramps to 650 DEG C after high-temperature calcination
Cell negative electrode material.
Embodiment 2
Carry out being sufficiently stirred for obtaining first during 1.5g gum arabics are added to 50mL water and 50mL ethylene glycol mixtures
Reactant liquor；In the first reactant liquor, the ammonium molybdate stirring 30min of addition 0.75g is completely dissolved to solid particle and obtains the second reaction
Liquid；The thiocarbamide of 0.6g is added into the second reactant liquor to be sufficiently stirred for 30min and target solution is obtained to grain dissolution, then by target
Solution is transferred in 200mL teflon-lined reactors after 150 DEG C of high-temperature storage 3h, obtains the first reactant, and first
Reactant is brown ceramic powder.
The first reactant is cleaned using deionized water and absolute ethyl alcohol, by the first reactant for completing to clean 60
Constant temperature 12h in DEG C drying box, the first reactant for completing freeze-day with constant temperature is proceeded in the atmosphere furnace of nitrogen～hydrogen gas mixture,
Atmosphere furnace obtains symmetrical matrix pore sphere micron calcium molybdate lithium ion with 1 DEG C/min ramps to 650 DEG C after high-temperature calcination
Cell negative electrode material.
Embodiment 3
Carry out being sufficiently stirred for obtaining first during 0.8g gum arabics are added to 30mL water and 30mL ethylene glycol mixtures
Reactant liquor；In the first reactant liquor, the ammonium molybdate stirring 20min of addition 0.4g is completely dissolved to solid particle and obtains the second reaction
Liquid；The thiocarbamide of 0.325g is added into the second reactant liquor to be sufficiently stirred for 30min and target solution is obtained to grain dissolution, then by mesh
Mark solution is transferred in 100mL teflon-lined reactors after 180 DEG C of high-temperature storage 1h, obtains the first reactant, the
One reactant is brown ceramic powder.
The first reactant is cleaned using deionized water and absolute ethyl alcohol, by the first reactant for completing to clean 60
Constant temperature 12h in DEG C drying box, the first reactant for completing freeze-day with constant temperature is proceeded in the atmosphere furnace of nitrogen-hydrogen mixed gas,
Atmosphere furnace obtains symmetrical matrix pore sphere micron calcium molybdate lithium ion with 1 DEG C/min ramps to 650 DEG C after high-temperature calcination
Cell negative electrode material.
To symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative is obtained in above-described embodiment 1 to embodiment 3
Material carries out performance test.
Fig. 3 is referred to, Fig. 3 is the ESEM of symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material
Figure (SEM).Sample obtains symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative into embodiment 3 for embodiment 1
Material.Wherein, the instrument used by sem analysis is the Quanta400F type projection electron microscopes of Dutch FEI Co., for observing
The microscopic appearance of specimen surface, accelerating potential is 10KV, and sample preparation is using being added dropwise in conducting resinl surface, air after absolute ethyl alcohol dispersion
Middle drying.Intuitively can know from Fig. 3, about 1.5 microns of the particle diameter of the molybdic acid calcium product of acquisition, obtained sample is in micro-
Rice is spherical, and spherical sample has two symmetrical matrix macropores at two ends, and pattern is highly uniform, good dispersion, particle diameter unification.
Fig. 4 is referred to, Fig. 4 is the projection Electronic Speculum of symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material
Figure (TEM).Sample obtains symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative into embodiment 3 for embodiment 1
Material.Wherein, the instrument used by tem analysis is the instrument that is usually used in prior art.From Fig. 4, further intuitively obtain
Know, about 1.5 microns of the particle diameter of the molybdic acid calcium product of acquisition, obtained sample are spherical in micron, and spherical sample is deposited at two ends
In two symmetrical matrix macropores, pattern is highly uniform, good dispersion, particle diameter unification.
Fig. 5 is referred to, Fig. 5 is the XRD spectrum of symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material.
Sample be embodiment 1 in obtain symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material.Wherein, XRD analysis
Instrument used characterizes the crystalline phase of prepared final product for Dutch PANalytical company Empyrean type X-ray diffractometers (XRD)
Structure.Test condition be Cu targets, K α radiation, 36kV, 30mA, step width 0.02o, 10～80o of sweep limits.Sample is placed in for powder
Sample stage groove is flattened, direct detection.As can be known from Fig. 3, the symmetrical matrix pore sphere micron calcium molybdate lithium that prepared by embodiment 1
Main peak of the ion battery cathode material in 2 θ=28.8 ° positions corresponds to (112) of calcium molybdate crystal (JCPD NO.29-0351)
Crystal face, the position of other diffraction maximums and intensity are also matched with corresponding PDF Ka Ku.It can also be seen that master from diffracting spectrum
Peak intensity is very high, and the peak shape of other diffraction maximums is also very sharp, while no miscellaneous peak, illustrates the calcium molybdate lithium of the preparation method synthesis
Ion battery cathode material crystallinity is good and purity is very high.Same test is carried out to embodiment 2 and embodiment 3, acquisition
As a result it is similar to, no longer states one by one.
Refer to Fig. 6, Fig. 6 is symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative to be obtained in embodiment 1
The XPS collection of illustrative plates of material, in collection of illustrative plates, (a) represents Ca elements, (b) represents Mo elements, (c) represents O elements, shows that the product for obtaining is true
Actually calcium molybdate.Wherein, the instrument used by XPS analysis characterizes material for the ESCALab250 types x-ray photoelectron spectroscopy in the U.S.
Material surface-element information.Same test is carried out to embodiment 2 and embodiment 3, the result of acquisition is similar to, no longer states one by one.
To the symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material obtained in embodiment 1 to embodiment 3
Material carries out electrochemical property test.
By symmetrical matrix pore sphere micron calcium molybdate and conductive agent, binding agent Vingon (PVDF) in mass ratio 7:
2: 1 quality is more uniform than ground and mixed to make electrode slice, and such as conductive agent is acetylene black, is, to electrode, to adopt with metal lithium sheet
Celgard2400 barrier films, electrolyte are EC: the 1mol/LiPF6 of DMC: DEC volume ratio 1: 1: 1, are assembled into buckle type lithium-ion electricity
Pond.Charge-discharge performance test is carried out with the Xin Wei Electronics Co., Ltd.s CT-3008-5V20mA-S4 type test systems of Shenzhen, is tested
Voltage range be 0.01V～3.0V.
The test result of specific discharge capacity is as follows：
The symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material obtained in embodiment 1 0.01～
Under 3.0V, 100mA/g current density, specific discharge capacity reaches 1029mAh/g, circulates specific discharge capacity through 50 times and is maintained at
435mAh/g, specifically, refers to Fig. 7 and Fig. 8.
The symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material obtained in embodiment 2 0.01～
Under 3.0V, 100mA/g current density, first discharge specific capacity reaches 997mAh/g, circulates specific discharge capacity through 50 times and keeps
In 434mAh/g.Specifically, refer to Fig. 9.
The symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material obtained in embodiment 3 0.01～
Under 3.0V, 100mA/g current density, first discharge specific capacity reaches 1018mAh/g, circulates specific discharge capacity through 50 times and keeps
In 438mAh/g.
It should be noted that in prior art, after molybdic acid calcium material circulates 50 times under 100mA/g current densities, electric discharge
Specific capacity is 276Ah/g.Obviously, the symmetrical matrix pore sphere micron that embodiment 1 is obtained into any embodiment in embodiment 3
The specific discharge capacity of calcium molybdate lithium ion battery negative material is above the specific discharge capacity of molybdic acid calcium material of the prior art.
The result of high rate performance test is as follows：
The symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material obtained in embodiment 1 is in current density
High rate performance test respectively under 50mA/g, 100mA/g, 200mA/g, 400mA/g and 200mA/g.Reversible capacity is respectively
551mAh/g, 525mAh/g, 506mAh/g mAh/g, 454mAh/g and 510mAh/g.
The symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material obtained in embodiment 2 is in current density
High rate performance test respectively under 50mA/g, 100mA/g, 200mA/g, 400mA/g and 200mA/g.Reversible capacity is respectively
545mAh/g, 521mAh/g, 503mAh/g mAh/g, 453mAh/g and 505mAh/g.
The symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material obtained in embodiment 3 is in current density
High rate performance test respectively under 50mA/g, 100mA/g, 200mA/g, 400mA/g and 200mA/g.Reversible capacity is respectively
534mAh/g、515mAh/g、501mAh/g mAh/g、451mAh/g、507mAh/g.Specifically, result is obtained such as in embodiment 3
Shown in Figure 10.
Symmetrical matrix pore sphere micron calcium molybdate lithium prepared by the result explanation said method of above-mentioned high rate performance test
Ion battery cathode material possesses preferable material invertibity and high rate performance, and then causes symmetrical matrix pore sphere micron molybdenum
Lithium ion battery prepared by sour calcium lithium ion battery negative material has preferable invertibity and high rate performance.
Above-mentioned electrochemical property test result shows, symmetrical matrix pore sphere micron calcium molybdate lithium prepared by said method
Ion battery cathode material specific capacity is higher, and electro-chemical activity is high, good reversibility, good cycle, with excellent storage lithium
Can, and then cause the specific volume of the lithium ion battery of symmetrical matrix pore sphere micron calcium molybdate lithium ion battery negative material preparation
Amount is higher, and electro-chemical activity is high, good reversibility, good cycle, with excellent storage lithium performance.
Each technical characteristic of embodiment described above arbitrarily can be combined, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more concrete and detailed, but and
Therefore can not be construed as limiting the scope of the patent.It should be pointed out that for one of ordinary skill in the art comes
Say, without departing from the inventive concept of the premise, some deformations and improvement can also be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (10)
1. a kind of preparation method of calcium molybdate lithium ion battery negative material, it is characterised in that comprise the steps：
Gum arabic, ammonium molybdate and the thiocarbamide of preset quality are sequentially added in the mixed solution of water and ethylene glycol, is fully stirred
Mix, obtain target solution；
In preset temperature range and Preset Time, hydro-thermal reaction is carried out to the target solution, obtain the first reactant；
First reactant is carried out washing, is dried and high-temperature calcination, symmetrical matrix pore sphere micron calcium molybdate lithium is obtained
Ion battery cathode material；
Wherein, the calcium content of the gum arabic is 0.02%～2%.
2. the preparation method of calcium molybdate lithium ion battery negative material according to claim 1, it is characterised in that it is described to
Gum arabic, ammonium molybdate and the thiocarbamide of preset quality are sequentially added in the mixed solution of water and ethylene glycol, is sufficiently stirred for, obtained
Target solution, comprises the steps：
The gum arabic of the first mass is added in the mixed solution of water and ethylene glycol, is sufficiently stirred for obtaining the first reactant liquor；
The ammonium molybdate of the second mass is added in first reactant liquor, is stirred to the ammonium molybdate and is completely dissolved that to obtain second anti-
Answer liquid；
The thiocarbamide of the 3rd mass is added in second reactant liquor, is stirred to the thiocarbamide and is completely dissolved that to obtain the target molten
Liquid.
3. the preparation method of calcium molybdate lithium ion battery negative material according to claim 1, it is characterised in that described mixed
The volume ratio for closing water and ethylene glycol in solution is 1: (0.9～1.2).
4. the preparation method of calcium molybdate lithium ion battery negative material according to claim 1, it is characterised in that Ah
The primary gummy mass ratio with the mixed solution is drawn to be 1: (5～150).
5. the preparation method of calcium molybdate lithium ion battery negative material according to claim 1, it is characterised in that the molybdenum
Sour ammonium is 1 with the mass ratio of the gum arabic: (1.3～2.1).
6. the preparation method of calcium molybdate lithium ion battery negative material according to claim 1, it is characterised in that the sulphur
Urea is 1 with the mass ratio of the ammonium molybdate: (0.9～6.1).
7. the preparation method of calcium molybdate lithium ion battery negative material according to claim 1, it is characterised in that described pre-
If temperature range is 150 DEG C～200 DEG C, the Preset Time is 30min～360min.
8. the preparation method of calcium molybdate lithium ion battery negative material according to claim 1, it is characterised in that described dry
Dry mode is to adopt constant temperature drying.
9. the preparation method of calcium molybdate lithium ion battery negative material according to claim 1, it is characterised in that the height
The temperature of temperature calcining is 500 DEG C～700 DEG C.
10. a kind of calcium molybdate lithium ion battery negative material, it is characterised in that the calcium molybdate lithium ion battery negative material by
In claim 1 to 9, the preparation method of calcium molybdate lithium ion battery negative material described in any one is prepared.
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