CN105762363A - Preparation method of ZIF complex based novel lithium ion battery cathode materials - Google Patents
Preparation method of ZIF complex based novel lithium ion battery cathode materials Download PDFInfo
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- H01M4/00—Electrodes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The invention discloses a preparation method of ZIF complex based novel lithium ion battery cathode materials.The preparation method has the advantages that a novel zeolitic imidazole organic framework compound is synthesized to prepare nitrogen-doped porous carbon materials which are applied to the lithium ion battery cathode materials, so that first specific discharge capacity reaches 1211 mAh/g, charge-discharge current density reaches 100 mA/g, and specific capacity is almost about 620 mAh/g (a theoretical value of commercial graphite cathode specific capacity reaching 372 mAh/g); even if the lithium ion battery cathode materials cycle for 100 times, good cycle performance can be demonstrated, and when current density reaches 1000 mAh/g, specific capacity can also reach 410 mAh/g, so that excellent rate performance can be demonstrated.
Description
Technical field
The invention belongs to the application of lithium ion battery negative material, belong to energy-storage function material, the preparation method being specifically related to a kind of Novel cathode material for lithium ion battery based on ZIF coordination compound.
Background technology
Since 21 century, along with the day by day exhaustion of the non-renewable as compound occupied by many households of Fossil fuel such as coal, oil, natural gas, and the problem of environmental pollution that its combustion zone comes, the energy and environmental problem have become as the significant bottleneck difficult problem affecting world today's sustainable development.In order to solve this world-famous puzzle, the renewable green energy resource seeking to substitute conventional fossil fuel just seems particularly urgent.Nineteen ninety, Japan sony and Moli company take the lead in release with carbon be negative pole lithium ion battery applications in commercialization.nullCompared to traditional lead-acid accumulator、The secondary cell such as nickel-cadmium cell and Ni-MH battery，Lithium ion battery has open-circuit voltage height, and (common commercial Li-ion battery running voltage is more than 2 times of other secondary cells，About 3.6V can be reached，And NI-G、The running voltage that ni-mh is general with plumbous battery only has 1.5V-2.0V)、Energy density is high, and (lithium ion battery is that in business-like secondary cell, energy density is maximum，Its volume energy density can reach 300Whdm-3，Mass energy density can also reach 100-140WhKg-1,It it is 2 times of NI-G Ni-MH battery energy density)、(lithium ion battery generally can circulate more than 600-1000 time long service life，It it is 2.5-10 times of lead-acid battery)、Safety superior (operating temperature range is-20 DEG C--+45 DEG C)、Environmental friendliness (contains poisonous lead with plumbic acid and nickel-cadmium cell、The materials such as cadmium are compared，Lithium ion battery is a kind of real green non-pollution environment-friendly battery)、Self discharge is little, and (lithium ion battery self-discharge rate monthly is only 6-8%，But the self-discharge rate of nickel-cadmium cell is approximately 20%、The self-discharge rate of Ni-MH battery is up to 30%，And there is memory effect in various degree，And lithium ion battery memory effect is almost nil，Therefore lithium ion battery can repeated charge use.) etc. advantage, and be considered as the classical energy of modern material and new forms of energy science.
The key components of lithium ion battery are positive pole, negative pole, barrier film.Negative material is as the important component part of lithium ion battery, and the chemical property of lithium ion battery is had conclusive impact by its Nomenclature Composition and Structure of Complexes.From the Development History of lithium ion battery, the development of negative material promotes lithium ion battery to enter commercialization stage.What initial lithium battery adopted is that lithium metal is as negative material, but lithium metal easily produces Li dendrite when discharge and recharge and causes the safety issues such as on fire or blast, then develop Zinc-lithium alloy material and solve above-mentioned safety issue, but alloy material is susceptible to volumetric expansion when embedding and removing, cause that cycle performance declines.Through further studying and comparing, have selected the graphited carbon commercialization negative material as lithium ion battery, up to now, business-like lithium ion battery negative material is still that graphited carbon, but graphitic carbon exists that specific capacity is low and the feature such as high rate performance difference, thus the exploitation of lithium ion battery negative material remains current focus.
At present, for in the research of lithium ion battery negative material, the research of carbons material is still that a focus, mainly concentrate on (the reference: 1, the Huanghai Sea is put down of Graphene aspect, Zhu person of outstanding talent. the preparation of new carbon Graphene and the application [J] in electrochemistry thereof. analytical chemistry, 2011,39 (7): 963-971；2、GuoH.-L.,WangX.-F.,QianQ.-Y.,etal.Agreenapproachtothesynthesisofgraphenenanosheets[J].ACSnano,2009,3(9):2653-2659；3, WangZ.-L., XuD., WangH.-G., etal.Insitufabricationofporousgrapheneelectrodesforhighp erformanceenergystorage [J] .ACSnano, 2013,7 (3): 2422-2430), but being still that at present and have no idea to prepare on a large scale Graphene, the research for Graphene is also be only limitted to the experimental stage.So promoting to prepare also just being particularly important of other kinds of porous carbon materials.Wherein utilizing metal organic framework compound to prepare porous carbon materials is exactly a good selection.Metal organic framework compound (MOFs) is as a kind of novel porous solid-state material, there is completely regular structure, the porosity of superelevation and specific surface area, and synthetic method is gentle, material choice enriches (different organic ligands just can form different structures), these features make it have the advantage that other materials is incomparable, and heterogeneous catalysis, gas storage and separate, the field such as optics, magnetic has important application.But in recent years metal organic framework compound is used for research (reference: the LiSL of clean energy resource aspect, XuQ.Metal organicframeworksasplatformsforcleanenergy [J] .Energy&EnvironmentalScience, 2013,6 (6): 1656-1683.) although few, but trend is good, and development space is very big.nullSince XuQiang (reference: JiangHL in 2010,LiuB,LanYQ,etal.Frommetal–organicframeworktonanoporouscarbon:towardaveryhighsurfaceareaandhydrogenuptake[J].JournaloftheAmericanChemicalSociety,2011,133 (31): 11854-11857.) seminar utilizes porous carbon materials prepared by metal organic framework compound to start for the research of ultracapacitor first，People begin to pay close attention to this novel method (reference: 1 preparing material with carbon element gradually、ZhengF,YangY,ChenQ.Highlithiumanodicperformanceofhighlynitrogen-dopedporouscarbonpreparedfromametal-organicframework[J].Naturecommunications,2014,5；2、ZuoL,ChenS,WuJ,etal.Facilesynthesisofthree-dimensionalporouscarbonwithhighsurfaceareabycalciningmetal–organicframeworkforlithium-ionbatteriesanodematerials[J].RSCAdvances,2014,4(106):61604-61610.).
In the present invention, MOFs (metal organic framework compound): be a class organic-inorganic hybrid material, organic ligand and inorganic metal cell formation form.
ZIF (imidazoles zeolites organic frame compound): belonging to a branch of metal organic framework compound, its organic ligand is mainly imidazoles and imidazoles analog, what a class of formation had a loose structure is similar to zeolite structured skeletonisation compound.
Self-discharge phenomenon: refer to that accumulator is when idle, also can consume electricity, and this phenomenon is called the self-discharge phenomenon of accumulator.Main cause is that inside battery there occurs irreversible reaction, thus causing the loss of battery capacity.
Li dendrite: refer to that the lithium battery adopting liquid electrolyte is when charging, the phenomenon of the dendritic metal lithium simple substance that lithium ion reduction is formed.
Specific capacity: be divided into weight ratio capacity and volume and capacity ratio, more be weight ratio capacity (unit is mAh/g), refer to the electricity that the battery of Unit Weight or active substance can be released.It it is the important symbol weighing battery performance quality.
High rate performance: under different electric current densities (such as 100mA/g, 1000mA/g etc.), battery is carried out discharge and recharge, (ratio) amount of capacity that battery shows, also it is the important symbol weighing battery performance quality, generally can along with the rising of charging and discharging currents density, specific capacity can decline.
Cycle performance is tested: refers to, under a certain electric current density, battery is carried out discharge and recharge, sees the impact on specific capacity of the discharge and recharge number of times.
Constant current charge-discharge is tested: be the inspection specific capacity height of rechargeable battery, multiplying power property, the isoparametric important means of cycle performance.
Summary of the invention
Goal of the invention: in order to solve the deficiencies in the prior art, the preparation method that the invention provides a kind of Novel cathode material for lithium ion battery based on ZIF coordination compound.
Technical scheme: the preparation method of a kind of Novel cathode material for lithium ion battery based on ZIF coordination compound, comprises the steps:
Step one: take ZnNO3·6H2O, 2-MIm (2-methylimidazole), 2,3-dipicolinic acid three kinds reactants, add water in the reactor that liner is politef material, described three kinds of reactant ZnNO3·6H2O, 2-MIm, 2,3-dipicolinic acid ratio be 1:1:1, described in the 1/4-3/4 that water is liner capacity that adds, at a certain temperature within the scope of 100 DEG C-160 DEG C, react two days, after with temperature be 1 DEG C/10min decrease speed be down to room temperature；
Step 2: take in step one crystal in reactor and, on sheet glass, select suitable crystal under the microscope, measure on " BrukerAPEX-IICCD " type monocrystalline instrument, obtain crystal data, utilizing software APEXII software to carry out data analysis, resolve crystal structure, chemical formula is [Zn6(2-MIm)10·2H2O], utilize Diamond software to carry out structure chart drafting；
Step 3: according to the method in step one, synthesizes presoma in a large number, after being down to room temperature, is filtered obtaining a large amount of pale yellow crystals；
Step 4: substantial amounts of crystal powder step 3 obtained, namely presoma, at inert atmosphere: calcine under nitrogen or argon, calcination temperature range is between 700 DEG C-900 DEG C, after reaching target temperature with the heating rate of 5 DEG C/min, under target temperature, stop 8h, its natural cooling of relief；
Step 5: carrying out soaking 36h with the hydrofluoric acid solution (FH) of 30% by the black solid powder obtained in step 4, period is changed FH twice and is stirred continuously, and washs with substantial amounts of water afterwards, until solution is in neutrality；
Step 6: pressed powder step 5 obtained is dried, and is applied in lithium ion battery negative material；
Step 7: the material obtained in step 6 is carried out dicing, makes lithium ion battery negative electrode；
Step 8: electrochemical property test: the voltage range in constant current charge-discharge test is 0.01V-3.0V, in during cycle performance test, charge-discharge test number of times is 100 times, electric current density is 100mA/g, high rate performance test has been respectively adopted at 100mA/g, 200mA/g, carry out constant current charge-discharge under 500mA/g, 1000mA/g, and under each multiplying power, cycle-index is 10 times.
As further optimization: the concrete operations of described step 6 are as follows: by black uniform with mass ratio 8:1:1 ground and mixed to cell negative electrode material and Kynoar (PVDF), conductive acetylene, with N-Methyl pyrrolidone (NMP) for solvent furnishing pulpous state, it is coated on Copper Foil, first dry 1h, then 120 DEG C of dry 10h in vacuum drying oven in the baking oven of 80 DEG C.
As further optimization: the concrete operations of described step 7 are as follows: with lithium sheet for electrode, PE (polyethylene) is diaphragm material, adopt the LiPF containing 1mol/L6It is the electrolyte of solvent for electrolyte, volume ratio EC:DEC:EMC=1:1:1, LiPF6Being lithium hexafluoro phosphate, EC is ethylene carbonate, EMC be Ethyl methyl carbonate, DEC is diethyl carbonate, and button cell model is 2025, carries out forming into button cell.
As further optimization: in described step one, take 0.1mmolZnNO3·6H2O, 0.1mmol2-MIm (2-methylimidazole), 0.1mmol2,3-dipicolinic acid, 5ml water is in the reactor that liner is politef material of 15ml.
Beneficial effect: the concrete advantage of the present invention is as follows:
(1) present invention is by synthesizing a kind of novel imidazoles zeolites organic frame compound, it is utilized to prepare the porous carbon materials of nitrating, and it is applied in the negative material of lithium ion battery, can reach first discharge specific capacity is 1211mAh/g, when charging and discharging currents density is 100mA/g, specific capacity is nearly all about 620mAh/g (and business-like graphite cathode specific capacity theoretical value is 372mAh/g), even circulating after 100 times, embody its good cycle performance, and when electric current density is 1000mA/g, specific capacity can also reach 410mAh/g, embody its good high rate performance.
(2) commercial Li-ion battery negative material is all adopt graphite type material at present, but its theoretical capacity only has 372mAh/g, largely limits the lithium ion battery development to electrical equipment.And the present invention is directed to the shortcoming of existing lithium cell cathode material, the present invention utilizes metal organic framework compound as the porous carbon materials of precursor power nitrating to obtain the Novel anode material with high specific capacity.
(3) in the present invention, negative material structure, specific surface area are adjustable, it is easy to realize the raising of negative material chemical property.Owing to the structure of presoma metal organic framework compound is adjustable with specific surface area, by selecting different calcining heats to realize the regulation and control of the structure to the porous carbon materials that calcining prepares.Avoid the structure unicity of existing graphitic carbon material, and then easily optimize the high performance lithium cell cathode material of acquisition.
(4), in the present invention, utilize the nitrogen heterocyclic ring frame complex that even structure is fixed as presoma, the uniformity of the lithium cell negative pole material nitrogen doped prepared after fully ensuring that calcining.While the specific capacity of such negative material obtains improving, cyclical stability is also guaranteed.
Accompanying drawing explanation
Fig. 1 is [Zn in the embodiment of the present invention 16(2-MIm)10·2H2O] tomograph；
Fig. 2 is [Zn in the embodiment of the present invention 16(2-MIm)10·2H2O] topological diagram；
Fig. 3 is the coordination compound [Zn obtained in the embodiment of the present invention 16(2-MIm)10·2H2O] XRD figure；
Fig. 4 is the XRD figure of the material with carbon element of the N doping obtained in the embodiment of the present invention 1；
Fig. 5 is the EDS figure of the material with carbon element of the N doping obtained in the embodiment of the present invention 1；
Fig. 6 is the SEM figure of the material with carbon element of the N doping obtained in the embodiment of the present invention 1；
Fig. 7 is the TEM figure of the material with carbon element of the N doping obtained in the embodiment of the present invention 1；
Fig. 8 is the cycle performance test figure of the negative material obtained in the embodiment of the present invention 1；
Fig. 9 is the high rate performance test figure of the negative material obtained in the embodiment of the present invention 1；
Figure 10 is the constant current charge-discharge curve test figure of the negative material obtained in the embodiment of the present invention 1.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.
Specific embodiment 1:
(1) preparation of negative material (material with carbon element of N doping)
Step one: take 0.1mmolZnNO3·6H2O, 0.1mmol2-MIm (2-methylimidazole), 0.1mmol2,3-dipicolinic acid, 5ml water is in the reactor that liner is politef material of 15ml, and the decrease speed being 1 DEG C/10min with temperature after reacting 2 days at temperature range 100-160 DEG C is down to room temperature.
Step 2: take in step one in reactor crystal on sheet glass, select suitable crystal under the microscope, " BrukerAPEX-IICCD " measurement on type monocrystalline instrument, obtain crystal data, software APEXII software is utilized to carry out data analysis, solving crystal structure, solving crystal-chemical formula is [Zn6(2-MIm)10·2H2O], utilize Diamond software to carry out structure chart drafting.Fig. 1: for the tomograph utilizing Diamond software to draw after APEXII software solves crystal structure.Fig. 2: for the three-dimensional topology figure utilizing Diamond software to draw after APEXII software solves crystal structure.
Step 3: according to the method in step one, synthesizes presoma in a large number, after being down to room temperature, is filtered obtaining a large amount of pale yellow crystals.Fig. 3: be a large amount of sample X-ray diffractograms after the operation of step 3, the diffraction pattern of substantial amounts of sample describing synthesis is consistent with the X-ray diffractogram of the sample through simulation.
Step 4: the substantial amounts of crystal powder (namely presoma) step 3 obtained is calcined under inert atmosphere (nitrogen or argon), calcination temperature range is 700-900 DEG C, after reaching target temperature with the heating rate of 5 DEG C/min, 8h, its natural cooling of relief is stopped under target temperature.
Step 5: carrying out soaking 36h with the hydrofluoric acid solution (FH) of 30% by the black solid powder obtained in step 4, period is changed FH twice and is stirred continuously, and washs with substantial amounts of water afterwards, until solution is in neutrality.The material with carbon element of N doping can be obtained after drying.Fig. 4: be that the material with carbon element to the N doping obtained carries out X-ray diffraction analysis, it can be seen that have a wide diffraction maximum at 23 °, for the characteristic peak of carbon.Also demonstrate that in the present invention, the material of preparation belongs to the category of material with carbon element.Fig. 5: be the scanning electron microscope (SEM) photograph of the material with carbon element of the N doping obtained after step 5 operates, it can be seen that material is belonging to micron level.Fig. 6: be the Flied emission transmission electron microscope picture of the material with carbon element of the N doping obtained after step 5 operates, it can be seen that Granular composite is almost uniform.Fig. 7: be the EDS figure of the nitrogen-doped carbon material obtained after step 5 operates, it can be seen that do not contained metallic zinc in sample after treatment, illustrated that metallic zinc has been fully processed totally, confirm that the material of preparation is the material with carbon element of N doping fully.
(2) preparation of electrode
Pressed powder step 5 obtained is dried, and is applied in lithium ion battery negative material.Namely: by black uniform with mass ratio 8:1:1 ground and mixed to cell negative electrode material and Kynoar (PVDF), conductive acetylene, with N-Methyl pyrrolidone (NMP) for solvent furnishing pulpous state, it is coated on Copper Foil, first dry 1h, then 120 DEG C of dry 10h in vacuum drying oven in the baking oven of 80 DEG C.It is then cut into sheet, makes lithium ion battery negative electrode.With lithium sheet for electrode, PE (polyethylene) is diaphragm material, and button cell model is 2025, carries out forming into button cell, then carries out electrochemical property test.
(3) electrode performance test
During test, temperature is room temperature, voltage range in constant current charge-discharge test is 0.01V-3.0V, in during cycle performance test, charge-discharge test number of times is 100 times, electric current density is 100mA/g, high rate performance test has been respectively adopted at 100mA/g, 200mA/g, 500mA/g, carry out constant current charge-discharge under 1000mA/g, and under each multiplying power, cycle-index is 10 times.Fig. 8 is when electric current density is 100mA/g, voltage range is the 0.01-3.0V specific capacity-cycle-index figure carrying out that constant current charge-discharge obtains, as can be seen from the figure, even specific capacity can also maintain about 620mAh/g after circulating 100 times, substantially without what decay, illustrate that in the present invention, the material of synthesis is good as lithium ion battery negative material cycle performance.Fig. 9 is to be 100mA/g respectively in electric current density, carry out constant current charge-discharge test under 200mA/g, 500mA/g, 1000mA/g and obtain high rate performance figure, and cycle-index is 10 times under each multiplying power, as can be seen from the figure in the present invention, the material high rate performance of synthesis is good.Figure 10 is when electric current density is 100mA/g, voltage range is the 0.01-3.0V voltage-specific volume spirogram carrying out that constant current charge-discharge obtains, as can be seen from the figure initial discharge specific capacity can reach 1211mAh/g, and discharge platform mainly concentrates on below 0.5V, and this meets the flash-over characteristic of common material with carbon element.
Specific embodiment 2
The preparation method of a kind of Novel cathode material for lithium ion battery based on ZIF coordination compound, comprises the steps:
Step one: take ZnNO3·6H2O, 2-MIm (2-methylimidazole), 2,3-dipicolinic acid three kinds reactants, add water in the reactor that liner is politef material, described three kinds of reactant ZnNO3·6H2O, 2-MIm, 2,3-dipicolinic acid ratio be 1:1:1, described in add water is liner capacity 1/4, at the temperature of 100 DEG C, react two days, after with temperature be 1 DEG C/10min decrease speed be down to room temperature.
Step 2: take in step one crystal in reactor and, on sheet glass, select suitable crystal under the microscope, measure on " BrukerAPEX-IICCD " type monocrystalline instrument, obtain crystal data, utilizing software APEXII software to carry out data analysis, resolve crystal structure, chemical formula is [Zn6(2-MIm)10·2H2O], utilize Diamond software to carry out structure chart drafting.
Step 3: according to the method in step one, synthesizes presoma in a large number, after being down to room temperature, is filtered obtaining a large amount of pale yellow crystals.
Step 4: substantial amounts of crystal powder step 3 obtained, namely presoma, at inert atmosphere: calcine under nitrogen or argon, calcining heat is 700 DEG C, after reaching target temperature with the heating rate of 5 DEG C/min, under target temperature, stop 8h, its natural cooling of relief.
Step 5: carrying out soaking 36h with the hydrofluoric acid solution (FH) of 30% by the black solid powder obtained in step 4, period is changed FH twice and is stirred continuously, and washs with substantial amounts of water afterwards, until solution is in neutrality.
Step 6: pressed powder step 5 obtained is dried, and it is applied in lithium ion battery negative material, concrete operations are as follows: by black uniform with mass ratio 8:1:1 ground and mixed to cell negative electrode material and Kynoar (PVDF), conductive acetylene, with N-Methyl pyrrolidone (NMP) for solvent furnishing pulpous state, it is coated on Copper Foil, first dry 1h, then 120 DEG C of dry 10h in vacuum drying oven in the baking oven of 80 DEG C.
Step 7: the material obtained in step 6 being carried out dicing, makes lithium ion battery negative electrode, concrete operations are as follows: with lithium sheet for electrode, PE (polyethylene) is diaphragm material, adopts the LiPF containing 1mol/L6It is the electrolyte of solvent for electrolyte, volume ratio EC:DEC:EMC=1:1:1, LiPF6Being lithium hexafluoro phosphate, EC is ethylene carbonate, EMC be Ethyl methyl carbonate, DEC is diethyl carbonate, and button cell model is 2025, carries out forming into button cell.
Step 8: electrochemical property test: the voltage range in constant current charge-discharge test is 0.01V, in during cycle performance test, charge-discharge test number of times is 100 times, electric current density is 100mA/g, high rate performance test has been respectively adopted at 100mA/g, 200mA/g, carry out constant current charge-discharge under 500mA/g, 1000mA/g, and under each multiplying power, cycle-index is 10 times.
Specific embodiment 3
The preparation method of a kind of Novel cathode material for lithium ion battery based on ZIF coordination compound, comprises the steps:
Step one: take ZnNO3·6H2O, 2-MIm (2-methylimidazole), 2,3-dipicolinic acid three kinds reactants, add water in the reactor that liner is politef material, described three kinds of reactant ZnNO3·6H2O, 2-MIm, 2,3-dipicolinic acid ratio be 1:1:1, described in add water is liner capacity 3/4, at the temperature of 160 DEG C, react two days, after with temperature be 1 DEG C/10min decrease speed be down to room temperature.
Step 2: take in step one crystal in reactor and, on sheet glass, select suitable crystal under the microscope, measure on " BrukerAPEX-IICCD " type monocrystalline instrument, obtain crystal data, utilizing software APEXII software to carry out data analysis, resolve crystal structure, chemical formula is [Zn6(2-MIm)10·2H2O], utilize Diamond software to carry out structure chart drafting.
Step 3: according to the method in step one, synthesizes presoma in a large number, after being down to room temperature, is filtered obtaining a large amount of pale yellow crystals.
Step 4: substantial amounts of crystal powder step 3 obtained, namely presoma, at inert atmosphere: calcine under nitrogen or argon, calcination temperature range is between 900 DEG C, after reaching target temperature with the heating rate of 5 DEG C/min, under target temperature, stop 8h, its natural cooling of relief.
Step 5: carrying out soaking 36h with the hydrofluoric acid solution (FH) of 30% by the black solid powder obtained in step 4, period is changed FH twice and is stirred continuously, and washs with substantial amounts of water afterwards, until solution is in neutrality.
Step 6: pressed powder step 5 obtained is dried, and it is applied in lithium ion battery negative material, concrete operations are as follows: by black uniform with mass ratio 8:1:1 ground and mixed to cell negative electrode material and Kynoar (PVDF), conductive acetylene, with N-Methyl pyrrolidone (NMP) for solvent furnishing pulpous state, it is coated on Copper Foil, first dry 1h, then 120 DEG C of dry 10h in vacuum drying oven in the baking oven of 80 DEG C.
Step 7: the material obtained in step 6 being carried out dicing, makes lithium ion battery negative electrode, concrete operations are as follows: with lithium sheet for electrode, PE (polyethylene) is diaphragm material, adopts the LiPF containing 1mol/L6It is the electrolyte of solvent for electrolyte, volume ratio EC:DEC:EMC=1:1:1, LiPF6Being lithium hexafluoro phosphate, EC is ethylene carbonate, EMC be Ethyl methyl carbonate, DEC is diethyl carbonate, and button cell model is 2025, carries out forming into button cell.
Step 8: electrochemical property test: the voltage range in constant current charge-discharge test is 3.0V, in during cycle performance test, charge-discharge test number of times is 100 times, electric current density is 100mA/g, high rate performance test has been respectively adopted at 100mA/g, 200mA/g, carry out constant current charge-discharge under 500mA/g, 1000mA/g, and under each multiplying power, cycle-index is 10 times.
Specific embodiment 4
The preparation method of a kind of Novel cathode material for lithium ion battery based on ZIF coordination compound, comprises the steps:
Step one: take ZnNO3·6H2O, 2-MIm (2-methylimidazole), 2,3-dipicolinic acid three kinds reactants, add water in the reactor that liner is politef material, described three kinds of reactant ZnNO3·6H2O, 2-MIm, 2,3-dipicolinic acid ratio be 1:1:1, described in add water is liner capacity 1/2, at the temperature of 130 DEG C, react two days, after with temperature be 1 DEG C/10min decrease speed be down to room temperature.
Step 2: take in step one crystal in reactor and, on sheet glass, select suitable crystal under the microscope, measure on " BrukerAPEX-IICCD " type monocrystalline instrument, obtain crystal data, utilizing software APEXII software to carry out data analysis, resolve crystal structure, chemical formula is [Zn6(2-MIm)10·2H2O], utilize Diamond software to carry out structure chart drafting.
Step 3: according to the method in step one, synthesizes presoma in a large number, after being down to room temperature, is filtered obtaining a large amount of pale yellow crystals.
Step 4: substantial amounts of crystal powder step 3 obtained, namely presoma, at inert atmosphere: calcine under nitrogen or argon, calcination temperature range is between 800 DEG C, after reaching target temperature with the heating rate of 5 DEG C/min, under target temperature, stop 8h, its natural cooling of relief.
Step 5: carrying out soaking 36h with the hydrofluoric acid solution (FH) of 30% by the black solid powder obtained in step 4, period is changed FH twice and is stirred continuously, and washs with substantial amounts of water afterwards, until solution is in neutrality.
Step 6: pressed powder step 5 obtained is dried, and it is applied in lithium ion battery negative material, concrete operations are as follows: by black uniform with mass ratio 8:1:1 ground and mixed to cell negative electrode material and Kynoar (PVDF), conductive acetylene, with N-Methyl pyrrolidone (NMP) for solvent furnishing pulpous state, it is coated on Copper Foil, first dry 1h, then 120 DEG C of dry 10h in vacuum drying oven in the baking oven of 80 DEG C.
Step 7: the material obtained in step 6 being carried out dicing, makes lithium ion battery negative electrode, concrete operations are as follows: with lithium sheet for electrode, PE (polyethylene) is diaphragm material, adopts the LiPF containing 1mol/L6It is the electrolyte of solvent for electrolyte, volume ratio EC:DEC:EMC=1:1:1, LiPF6Being lithium hexafluoro phosphate, EC is ethylene carbonate, EMC be Ethyl methyl carbonate, DEC is diethyl carbonate, and button cell model is 2025, carries out forming into button cell.
Step 8: electrochemical property test: the voltage range in constant current charge-discharge test is 2.0V, in during cycle performance test, charge-discharge test number of times is 100 times, electric current density is 100mA/g, high rate performance test has been respectively adopted at 100mA/g, 200mA/g, carry out constant current charge-discharge under 500mA/g, 1000mA/g, and under each multiplying power, cycle-index is 10 times.
The present invention is not limited to above-mentioned preferred forms; anyone can draw other various forms of products under the enlightenment of the present invention; no matter but in its shape or structure, do any change, every have same or like with the application like technical scheme, all fall within protection scope of the present invention.
Claims (4)
1. the preparation method based on the Novel cathode material for lithium ion battery of ZIF coordination compound, it is characterised in that: comprise the steps:
Step one: take ZnNO3·6H2O, 2-MIm (2-methylimidazole), 2,3-dipicolinic acid three kinds reactants, add water in the reactor that liner is politef material, described three kinds of reactant ZnNO3·6H2O, 2-MIm, 2,3-dipicolinic acid ratio be 1:1:1, described in the 1/4-3/4 that water is liner capacity that adds, at a certain temperature within the scope of 100 DEG C-160 DEG C, react two days, after with temperature be 1 DEG C/10min decrease speed be down to room temperature；
Step 2: take in step one crystal in reactor and, on sheet glass, select suitable crystal under the microscope, measure on " BrukerAPEX-IICCD " type monocrystalline instrument, obtain crystal data, utilizing software APEXII software to carry out data analysis, resolve crystal structure, chemical formula is [Zn6(2-MIm)10·2H2O], utilize Diamond software to carry out structure chart drafting；
Step 3: according to the method in step one, synthesizes presoma in a large number, after being down to room temperature, is filtered obtaining a large amount of pale yellow crystals；
Step 4: substantial amounts of crystal powder step 3 obtained, namely presoma, at inert atmosphere: calcine under nitrogen or argon, calcination temperature range is between 700 DEG C-900 DEG C, after reaching target temperature with the heating rate of 5 DEG C/min, under target temperature, stop 8h, its natural cooling of relief；
Step 5: carrying out soaking 36h with the hydrofluoric acid solution (FH) of 30% by the black solid powder obtained in step 4, period is changed FH twice and is stirred continuously, and washs with substantial amounts of water afterwards, until solution is in neutrality；
Step 6: pressed powder step 5 obtained is dried, and is applied in lithium ion battery negative material；
Step 7: the material obtained in step 6 is carried out dicing, makes lithium ion battery negative electrode；
Step 8: electrochemical property test: the voltage range in constant current charge-discharge test is 0.01V-3.0V, in during cycle performance test, charge-discharge test number of times is 100 times, electric current density is 100mA/g, high rate performance test has been respectively adopted at 100mA/g, 200mA/g, carry out constant current charge-discharge under 500mA/g, 1000mA/g, and under each multiplying power, cycle-index is 10 times.
2. the preparation method of the Novel cathode material for lithium ion battery based on ZIF coordination compound according to claim 1, it is characterized in that: the concrete operations of described step 6 are as follows: by black uniform with mass ratio 8:1:1 ground and mixed to cell negative electrode material and Kynoar (PVDF), conductive acetylene, with N-Methyl pyrrolidone (NMP) for solvent furnishing pulpous state, it is coated on Copper Foil, first dry 1h, then 120 DEG C of dry 10h in vacuum drying oven in the baking oven of 80 DEG C.
3. the preparation method of the Novel cathode material for lithium ion battery based on ZIF coordination compound according to claim 1, it is characterized in that: the concrete operations of described step 7 are as follows: with lithium sheet for electrode, PE (polyethylene) is diaphragm material, adopts the LiPF containing 1mol/L6It is the electrolyte of solvent for electrolyte, volume ratio EC:DEC:EMC=1:1:1, LiPF6Being lithium hexafluoro phosphate, EC is ethylene carbonate, EMC be Ethyl methyl carbonate, DEC is diethyl carbonate, and button cell model is 2025, carries out forming into button cell.
4. the preparation method of the Novel cathode material for lithium ion battery based on ZIF coordination compound according to claim 1, it is characterised in that: in described step one, take 0.1mmolZnNO3·6H2O, 0.1mmol2-MIm (2-methylimidazole), 0.1mmol2,3-dipicolinic acid, 5ml water is in the reactor that liner is politef material of 15ml.
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