CN117977025A - Nitrogen-doped conductive molybdenum carbide lithium oxalate composite lithium supplementing agent, and preparation method and application thereof - Google Patents
Nitrogen-doped conductive molybdenum carbide lithium oxalate composite lithium supplementing agent, and preparation method and application thereof Download PDFInfo
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- molybdenum carbide
- lithium oxalate
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- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 title claims abstract description 69
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 61
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910039444 MoC Inorganic materials 0.000 title claims abstract description 53
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000001694 spray drying Methods 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 18
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 10
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 10
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 10
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 10
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- -1 molybdenum lithium carbonate Chemical compound 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 230000002829 reductive effect Effects 0.000 abstract description 6
- 238000006722 reduction reaction Methods 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 abstract 2
- 238000005303 weighing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000004576 sand Substances 0.000 description 5
- 239000013589 supplement Substances 0.000 description 5
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000002083 X-ray spectrum Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910011140 Li2C2 Inorganic materials 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- MOOYSSSIVSFZQA-UHFFFAOYSA-N [Li].[Mo] Chemical compound [Li].[Mo] MOOYSSSIVSFZQA-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a nitrogen-doped conductive molybdenum carbide lithium oxalate composite lithium supplementing agent, and a preparation method and application thereof. According to the invention, C3N4 and ammonium molybdate are mixed and sanded in a specific proportion, a precursor is obtained through spray drying, reduction and carbonization treatment are carried out in an inert atmosphere to obtain the nitrogen-doped conductive molybdenum carbide catalyst, lithium oxalate is sanded to obtain nano lithium oxalate, and the nano lithium oxalate are dispersed and mixed in a specific proportion and then spray-dried to obtain the nano lithium oxalate. The battery containing the composite lithium supplementing agent is further subjected to a charge-discharge experiment, the battery not only shows higher lithium supplementing capacity, but also reduces the decomposition voltage to 4.12V, and the full battery of D-NCM622-M1 Gr and D-NCM622-M1 SiC prepared by the composite lithium supplementing agent is subjected to the charge-discharge experiment, so that the first capacity of the full battery is obviously improved, and the active lithium loss is reduced to below 18%.
Description
Technical Field
The invention relates to the technical field of composite lithium supplementing materials, in particular to a nitrogen-doped conductive molybdenum carbide lithium oxalate composite lithium supplementing agent, and a preparation method and application thereof.
Background
The gas-releasing positive electrode lithium supplement (Li 2O、Li3N、Li2C2O4、Li2C4O4) is considered to be a very valuable positive electrode lithium supplement to be applied thanks to its advantages of no residue and high pre-lithiation capacity comparable to lithium metal, lithium oxalate exhibiting sufficient advantages in terms of cost and stability compared to the preparation condition limitations of Li 2 O and Li 3 N instability (inert gas protection). However, since lithium oxalate is subject to its low conductivity and electrochemical activity, resulting in its decomposition potential as high as 4.7V, it presents a serious challenge to the cathode material and electrolyte when applied, and thus, a modification strategy for enhancing the electrochemical activity of lithium oxalate needs to be proposed.
Typically, accelerating charge transfer and reducing the reaction energy barrier can effectively improve electrochemical activity, and the introduction of high-activity conductive agents and catalysts can significantly improve the application prospect of Li 2C2O4. At present, although some technologies propose to reduce the potential of Li 2C2O4 by using a composite catalyst, the preparation technology is not beneficial to industrial scale-up, and uniformity and consistency are still under great test.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the invention provides the conductive molybdenum lithium oxalate composite lithium supplementing agent of carbon nitride, which has low decomposition potential, good lithium supplementing effect and easy guarantee of uniformity and consistency in industrial scale-up production.
The invention adopts the following technical scheme: the preparation of the nitrogen-doped conductive molybdenum carbide lithium oxalate composite lithium supplementing agent comprises the following steps:
Dissolving a C3N4 material and ammonium molybdate in a mass ratio of (3-6) (1-3) in water, sanding, performing spray drying to obtain a Mo-C3N4 precursor, and then performing reduction and carbonization treatment on the precursor in an inert atmosphere to obtain the nitrogen-doped conductive molybdenum carbide catalyst;
dissolving lithium oxalate in water, and then sanding to prepare nano lithium oxalate;
And (3) dispersing and dissolving the nano lithium oxalate and the nitrogen doped conductive molybdenum carbide catalyst in water according to the mass ratio of (5-10) to (1-2), and performing spray drying to obtain the nano lithium oxalate and nitrogen doped conductive molybdenum carbide catalyst.
The invention also provides application of the composite lithium supplementing agent in the lithium supplementing agent of the positive electrode of the lithium battery.
The invention also provides a lithium battery, and the positive electrode material of the lithium battery comprises the composite lithium supplementing agent.
Compared with the prior art, the invention has the core effects that: according to the invention, C3N4 and ammonium molybdate are mixed and sanded in a specific proportion, a precursor is obtained through spray drying, reduction and carbonization treatment are carried out in an inert atmosphere to obtain the nitrogen-doped conductive molybdenum carbide catalyst, lithium oxalate is sanded to obtain nano lithium oxalate, and the nano lithium oxalate and ammonium molybdate are dispersed and mixed in a specific proportion and then are prepared through spray drying.
And further charging the battery containing the composite lithium supplementing agent to 4.7V at the rate of 50 mA/g and discharging to 3V at the rate of 50 mA/g, so that the battery shows higher lithium supplementing capacity and the decomposition voltage is reduced to 4.12V; the D-NCM622-M1 Gr and D-NCM622-M1 SiC full batteries prepared by the composite lithium supplementing agent are charged to 4.5V at the rate of 50 mA/g and discharged to 2.8V at the rate of 50 mA/g, the primary capacity of the full batteries is obviously improved, the loss of active lithium can be reduced to below 18%, and the lithium supplementing effect is good.
Drawings
FIG. 1 is an X-ray spectrum of nitrogen doped conductive molybdenum carbide of example 1 of the present invention;
FIG. 2 is a projection electron microscope image of the nitrogen doped conductive molybdenum carbide of example 1 of the present invention;
FIG. 3 is a graph showing the particle size analysis of molybdenum carbide in the nitrogen-doped conductive molybdenum carbide according to example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of sanded nano lithium oxalate in example 1 of the present invention;
FIG. 5 is an X-ray spectrum of a nitrogen-doped conductive molybdenum carbide lithium oxalate composite lithium supplement in example 1 of the present invention;
FIG. 6 is a scanning electron microscope image of a nitrogen-doped conductive molybdenum carbide lithium oxalate composite lithium supplement of example 1 of the present invention;
FIG. 7 is a graph of the first charge and discharge of D-M1 and D-R1;
FIG. 8 is an exploded potential diagram of D-M1 and D-R1;
FIG. 9 is a graph of the first charge and discharge of D-NCM622 Gr and D-NCM622-M1 Gr;
FIG. 10 is a graph of the first charge and discharge of D-NCM 622-SiC and D-NCM622-M1 SiC.
Detailed Description
The invention provides a nitrogen-doped conductive molybdenum carbide lithium oxalate composite lithium supplementing agent, which is prepared by the following steps:
Dissolving a C3N4 material and ammonium molybdate in a mass ratio of (3-6) (1-3) in water, sanding, performing spray drying to obtain a Mo-C3N4 precursor, and then performing reduction and carbonization treatment on the precursor in an inert atmosphere to obtain the nitrogen-doped conductive molybdenum carbide catalyst;
dissolving lithium oxalate in water, and then sanding to prepare nano lithium oxalate;
And (3) dispersing and dissolving the nano lithium oxalate and the nitrogen doped conductive molybdenum carbide catalyst in water according to the mass ratio of (5-10) to (1-2), and performing spray drying to obtain the nano lithium oxalate and nitrogen doped conductive molybdenum carbide catalyst.
As a preferable implementation mode, the C3N4 material is prepared by preserving heat for 4-8 hours at 400-600 ℃ by cyanamide or melamine or urea. Further preferably, the heating rate of the C3N4 material during preparation is 2-5 ℃/min.
As a preferred embodiment, the conditions for the precursor reductive carbonization treatment are: heating to 700-900 ℃ at a speed of 5-10 ℃/min, and preserving heat for 2-5 h.
As a preferred embodiment, the nitrogen-doped conductive molybdenum carbide catalyst has a lamellar structure, the size is 1-4 nm, and the particle size of the sanded nano lithium oxalate is 200-500 nm.
As a preferable embodiment, the concentration of the lithium oxalate solution is 0.02-0.08 g/mL when sanding.
As a preferable implementation mode, the sanding time of the lithium oxalate is 1-3 hours.
As a preferred embodiment, the spray drying condition is 120-200 ℃ and the rate is 0.5-2L/h.
The invention also provides application of the composite lithium supplementing agent in the lithium supplementing agent of the positive electrode of the lithium battery.
The invention also provides a lithium battery, and the positive electrode material of the lithium battery comprises the composite lithium supplementing agent.
The present invention will be described in further detail with reference to specific examples so as to more clearly understand the present invention by those skilled in the art.
The following examples are given for illustration of the invention only and are not intended to limit the scope of the invention. All other embodiments obtained by those skilled in the art without creative efforts are within the protection scope of the present invention based on the specific embodiments of the present invention.
In the examples of the present invention, all raw material components are commercially available products well known to those skilled in the art unless specified otherwise; in the embodiments of the present invention, unless specifically indicated, all technical means used are conventional means well known to those skilled in the art.
Example 1
The embodiment provides a preparation method of a nitrogen-doped conductive molybdenum carbide lithium oxalate composite lithium supplementing agent, which comprises the following steps:
Step S1, weighing 12g of melamine, placing the melamine in a crucible with a cover, then placing the crucible in a muffle furnace, heating to 550 ℃ at 2.5 ℃ per minute under an air atmosphere, and preserving heat for 6 hours to obtain C3N4. 4g of C3N4 and 2g of ammonium molybdate were weighed and dispersed in water, followed by spray drying to obtain a Mo-C3N4 precursor, the spray drying temperature being 200℃and the flow rate being 1L/h. And heating the Mo-C3N4 precursor to 800 ℃ in a high-temperature furnace protected by Ar at a speed of 10 ℃ per minute, and preserving heat for 2 hours to obtain the nitrogen-doped conductive molybdenum carbide catalyst. The X-ray diffraction pattern is shown in figure 1 (PDF #89-2868 in figure 1 represents PDF card number of standard molybdenum carbide), the morphology is shown in figure 2, and the size of the molybdenum carbide is shown in figure 3.
And S2, weighing 50g of commercial lithium oxalate, dissolving in 1L of water, pouring into a sand mill, and sanding for 1h to obtain nano lithium oxalate, wherein the morphology is shown in figure 4.
And step S3, weighing 5g of lithium oxalate (based on the mass of pure lithium oxalate) in the step S2 and 1g of the nitrogen-doped conductive molybdenum carbide catalyst in the step S1, uniformly dispersing in water, and then spray-drying the prepared mixed solution to obtain the nitrogen-doped conductive molybdenum carbide lithium oxalate composite lithium supplementing agent M1, wherein the spray-drying temperature is 200 ℃ and the flow rate is 1L/h. The X-ray spectrum is shown in FIG. 5 (PDF #89-2868 and PDF #24-0646 in FIG. 5 represent PDF card numbers of standard molybdenum carbide and lithium oxalate respectively), and the morphology is shown in FIG. 6.
Example 2
The embodiment provides a preparation method of a nitrogen-doped conductive molybdenum carbide lithium oxalate composite lithium supplementing agent, which comprises the following steps:
Step S1: 12 g melamine is weighed and placed in a crucible with a cover, then the crucible is placed in a muffle furnace, and the temperature is raised to 600 ℃ at 5 ℃ per minute under the air atmosphere, and the C3N4 is obtained by heat preservation of 8: 8 h. 4 g of C3N4 and 2 g ammonium molybdate were weighed and dispersed in water, followed by spray drying to obtain a Mo-C3N4 precursor, the spray drying temperature being 150℃and the flow rate being 1L/h. And heating the Mo-C3N4 precursor to 900 ℃ in an Ar protected high-temperature furnace at 10 ℃/min, and preserving heat for 5h to prepare the nitrogen-doped conductive molybdenum carbide catalyst.
Step S2: weighing 50 g commercial lithium oxalate, dissolving in 1L water, pouring into a sand mill, and sanding 3h to obtain nano lithium oxalate.
Step S3: and (3) weighing 8g lithium oxalate (based on the mass of pure lithium oxalate) and 1 g nitrogen-doped conductive molybdenum carbide catalyst, uniformly dispersing in water, and then spray-drying the prepared mixed solution to obtain the nitrogen-doped conductive molybdenum carbide lithium oxalate composite lithium supplementing agent M2, wherein the spray-drying temperature is 120 ℃, and the flow rate is 1L/h.
Comparative example 1
50G of commercial lithium oxalate is weighed and dissolved in 1L of water, and poured into a sand mill to be sanded for 3 hours, so as to obtain nano lithium oxalate R1.
Comparative example 2
And 5g of commercial lithium oxalate and 1g of molybdenum carbide to prepare the molybdenum carbide lithium oxalate composite lithium supplementing agent R2, wherein the molybdenum carbide is prepared by ball milling for 3 hours and then composite sintering.
Comparative example 3
The comparative example provides a preparation method of a nitrogen-doped conductive molybdenum carbide lithium oxalate composite lithium supplementing agent, which comprises the following steps:
Step S1: 12 g melamine is weighed and placed in a crucible with a cover, then the crucible is placed in a muffle furnace, the temperature is increased to 550 ℃ at 2.5 ℃ per minute under the air atmosphere, and the temperature is kept at 6 h to obtain C3N4. 4g of C3N4 and 2 g ammonium molybdate were weighed and dispersed in water, followed by spray drying to obtain a Mo-C3N4 precursor, the spray drying temperature being 200℃and the flow rate being 1L/h. And heating the Mo-C3N4 precursor to 800 ℃ in a high-temperature furnace protected by Ar at a speed of 10 ℃ per minute, and preserving heat for 2 h to prepare the nitrogen-doped conductive molybdenum carbide catalyst.
Step S2: weighing 50 g commercial lithium oxalate, dissolving in 1L water, pouring into a sand mill, and sanding 3h to obtain nano lithium oxalate.
Step S3: 5g of nano lithium oxalate, 1g of nitrogen doped conductive molybdenum carbide, and 3h g of ball milling for compounding to prepare the molybdenum carbide lithium oxalate compound lithium supplementing agent R3.
Comparative example 4
The comparative example provides a preparation method of a nitrogen-doped conductive molybdenum carbide lithium oxalate composite lithium supplementing agent, which comprises the following steps:
Step S1: 12 g melamine is weighed and placed in a crucible with a cover, then the crucible is placed in a muffle furnace, the temperature is increased to 550 ℃ at 2.5 ℃ per minute under the air atmosphere, and the temperature is kept at 6h to obtain C3N4. 10 g of C3N4 and 1 g ammonium molybdate were weighed and dispersed in water, followed by spray drying to obtain a Mo-C3N4 precursor, the spray drying temperature being 200℃and the flow rate being 1L/h. And heating the Mo-C3N4 precursor to 800 ℃ in a high-temperature furnace protected by Ar at a speed of 10 ℃ per minute, and preserving heat for 2h to prepare the R molybdenum carbide catalyst.
Step S2: weighing 50 g commercial lithium oxalate, dissolving in 1L water, pouring into a sand mill, and sanding 3h to obtain nano lithium oxalate.
Step S3: and (3) weighing 5g lithium oxalate and 1 g R molybdenum carbide catalyst, uniformly dispersing in water, and then uniformly spray-drying the prepared mixed solution to obtain the nitrogen-doped conductive molybdenum carbide lithium oxalate composite lithium supplementing agent R4, wherein the spray-drying temperature is 120 ℃, and the flow rate is 1L/h.
Performance test:
The materials in examples and comparative examples were identified as active material 9: conductive agent 0.5: the binder ratio of 0.5 was formed into a mixed slurry in NMP (nitrogen-methylpyrrolidone), and then the slurry was uniformly coated on a carbon-coated aluminum foil or LiNi0.6Co0.2Mn0.2O2 (NCM 622) electrode, and after vacuum drying at 110℃for 12 h, electrodes D-M1, D-M2, D-R1, D-R2, D-R3, D-R4, D-NCM622-M1 were obtained.
The battery was assembled with D-M1, D-M2, D-R1, D-R2, D-R3, and D-R4 as working electrodes and lithium metal as counter electrodes, and charge and discharge tests were performed by dissolving 1mol of lithium hexafluorophosphate (LiPF 6) in 1L of a mixed solvent of Ethylene Carbonate (EC) and ethylmethyl carbonate (EMC) (solvent volume ratio of 3:7), 5wt% of fluoroethylene carbonate (FEC) as an additive, and PP (polypropylene) as a separator.
The full cell was assembled and tested for charge and discharge using D-NCM622-M1 as the working electrode, graphite (Gr) or silicon carbon (SiC) negative electrode as the counter electrode, 1mol lithium hexafluorophosphate (LiPF 6) as the electrolyte solution, 5 wt% fluoroethylene carbonate (FEC) as the additive and PP (polypropylene) as the separator, in a mixed solvent of 1L Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) (solvent volume ratio 3:7).
(1) The cells with D-M1, D-M2, D-R1, D-R2, D-R3 and D-R4 as working electrodes were first charged to 4.7: 4.7V at 50 mA/g and then discharged to 3: 3V at 50 mA/g. The first charge capacity pair is shown in table 1.
TABLE 1
From the above results, it was found that all of lithium oxalate in D-M1 and D-M2 was decomposed by the nitrogen-doped conductive molybdenum carbide catalyst, and a high lithium supplementing capacity was exhibited, and the decomposition voltage was reduced to 4.12V. The D-R1 has no catalytic effect, the D-R2 and the D-R3 have no or non-uniform catalyst effect, the lithium oxalate is partially decomposed, the lithium supplementing capacity is limited, and the decomposition voltage is more than 4.6V. The R molybdenum carbide prepared by the D-R4 outside the optimized proportion has low activity, high lithium release voltage and limited capacity exertion (shown in figures 7 and 8).
(2) Full cells of D-NCM622-M1||Gr and D-NCM622-M1||SiC were charged to 4.5V at 50 mA/g and then discharged to 2.8V at 50 mA/g. The first charge-discharge capacity improvement and active lithium loss are shown in table 2.
TABLE 2
As can be seen from table 2, the addition of the nitrogen doped conductive molybdenum lithium carbide oxalate composite lithium supplement significantly improved the initial capacity of the full cell and reduced the active lithium loss (as shown in fig. 9 and 10).
It should be noted that the above examples are only for further illustrating and describing the technical solution of the present invention, and are not intended to limit the technical solution of the present invention, and the method of the present invention is only a preferred embodiment and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the nitrogen-doped conductive molybdenum carbide lithium oxalate composite lithium supplementing agent is characterized by comprising the following steps of:
Dissolving a C3N4 material and ammonium molybdate in a mass ratio of (3-6) (1-3) in water, sanding, performing spray drying to obtain a Mo-C3N4 precursor, and then performing reduction and carbonization treatment on the precursor in an inert atmosphere to obtain the nitrogen-doped conductive molybdenum carbide catalyst;
dissolving lithium oxalate in water, and then sanding to prepare nano lithium oxalate;
And (3) dispersing and dissolving the nano lithium oxalate and the nitrogen doped conductive molybdenum carbide catalyst in water according to the mass ratio of (5-10) to (1-2), and performing spray drying to obtain the nano lithium oxalate and nitrogen doped conductive molybdenum carbide catalyst.
2. The nitrogen-doped conductive molybdenum lithium carbonate composite lithium carbonate supplementing agent according to claim 1, wherein the C3N4 material is prepared by heat preservation of cyanamide or melamine or urea at 400-600 ℃ for 4-8 hours.
3. The nitrogen-doped conductive molybdenum lithium carbonate composite lithium carbonate supplementing agent according to claim 2, wherein the heating rate of the C3N4 material is 2-5 ℃/min.
4. The nitrogen-doped conductive molybdenum lithium oxalate composite lithium supplementing agent according to claim 1, wherein the conditions of the precursor reduction carbonization treatment are as follows: heating to 700-900 ℃ at a speed of 5-10 ℃/min, and preserving heat for 2-5 h.
5. The nitrogen-doped conductive molybdenum carbide lithium oxalate composite lithium supplementing agent according to claim 1, wherein the nitrogen-doped conductive molybdenum carbide catalyst is of a lamellar structure, and the size of molybdenum carbide is 1-4 nm; the grain diameter of the nanometer lithium oxalate after sanding is 200-500 nm.
6. The nitrogen-doped conductive molybdenum lithium oxalate composite lithium supplementing agent according to claim 1, wherein the concentration of the lithium oxalate solution is 0.02-0.08 g/mL during sanding.
7. The nitrogen-doped conductive molybdenum carbide lithium oxalate composite lithium supplementing agent according to claim 1, wherein the sanding time of lithium oxalate is 1-3 h.
8. The nitrogen-doped conductive molybdenum lithium oxalate composite lithium supplementing agent according to claim 1, wherein the spray drying condition is 120-200 ℃ and the rate is 0.5-2L/h.
9. The use of the composite lithium-supplementing agent according to any one of claims 1 to 8 in a lithium battery positive electrode lithium-supplementing agent.
10. A lithium battery, characterized in that the positive electrode material comprises the composite lithium supplementing agent according to any one of claims 1 to 8.
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