CN105762363B - A kind of preparation method of the lithium ion battery negative material based on ZIF complexs - Google Patents
A kind of preparation method of the lithium ion battery negative material based on ZIF complexs Download PDFInfo
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
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- 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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- 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 kind of preparation methods of the novel cathode material for lithium ion battery based on ZIF complexs.The present invention is by synthesizing a kind of novel imidazoles zeolites organic frame compound, the porous carbon materials of nitrating are prepared using it, and it is applied in the negative material of lithium ion battery, first discharge specific capacity can be reached for 1211mAh/g, when charging and discharging currents density is 100mA/g, specific capacity is nearly all 620mAh/g or so (and commercialized graphite cathode specific capacity theoretical value is 372mAh/g), even after cycle 100 times, embody its good cycle performance, and when current density is 1000mA/g, specific capacity can also reach 410mAh/g, embody its good high rate performance.
Description
Technical field
The invention belongs to the application fields of lithium ion battery negative material, belong to energy-storage function material, and in particular to a kind of
The preparation method of lithium ion battery negative material based on ZIF complexs.
Background technology
Since 21 century, with increasingly exhausted, the Yi Jiqi of the non-renewable a compound occupied by many households of the fossil fuels such as coal, oil, natural gas
The problem of environmental pollution that combustion zone comes, energy and environmental problem have become the significant bottleneck for influencing world today's sustainable development
Property problem.In order to solve this world-famous puzzle, seeking to substitute the renewable green energy resource of conventional fossil fuel just seems particularly urgent
It cuts.Nineteen ninety, it is the lithium ion battery applications of cathode in commercialization that Japanese sony and Moli companies, which take the lead in releasing using carbon,.Compared to
The secondary cells such as traditional lead-acid accumulator, nickel-cadmium cell and Ni-MH battery, lithium ion battery are high (common with open-circuit voltage
Commercial Li-ion battery operating voltage is other secondary cells more than 2 times, can reach 3.6V or so, and ni-Cd, ni-mh and
The general operating voltage of lead battery only has 1.5V-2.0V), high (lithium ion battery is in commercialized secondary cell to energy density
Energy density maximum, volume energy density can reach 300Wh dm-3, and mass energy density can also reach 100-
140WhKg-1 is 2 times of ni-Cd Ni-MH battery energy density), (lithium ion battery can generally recycle 600- to service life length
1000 times or more, be 2.5-10 times of lead-acid battery), safety superior (operating temperature range is -20 DEG C --+45 DEG C), environment
It is friendly that (compared with plumbic acid and nickel-cadmium cell contain the substances such as toxic lead, cadmium, lithium ion battery is a kind of real green without dirt
Contaminate environment-friendly battery), small (self-discharge rate of lithium ion battery monthly is only 6-8%, but the self-discharge rate of nickel-cadmium cell for self discharge
About 20%, the self-discharge rate of Ni-MH battery is up to 30%, and with different degrees of memory effect, and to lithium-ion electric
Memory effect is almost nil for pond, therefore lithium ion battery can be used with repeated charge.) the advantages that, and be considered existing
For material and the classical energy of new energy science.
The key components of lithium ion battery are anode, cathode, diaphragm.Negative material is as the important of lithium ion battery
Component part, the Nomenclature Composition and Structure of Complexes have decisive impact the chemical property of lithium ion battery.From lithium ion battery
Development History sees that the development of negative material promotes lithium ion battery to enter commercialization stage.Initial lithium battery is using gold
Belong to lithium as negative material, but lithium metal easily generates Li dendrite in charge and discharge and the safeties such as on fire or explosion is caused to be asked
Topic, then develops Zinc-lithium alloy material and solves above-mentioned safety issue, but alloy material is easily sent out in embedding and removing
Raw volume expansion, causes cycle performance to decline.By further studying and comparing, graphited carbon has been selected as lithium ion
The commercialization negative material of battery, up to now, commercialized lithium ion battery negative material is still graphited carbon, still
Graphitic carbon is there are the features such as specific capacity is low and high rate performance is poor, thus the exploitation of lithium ion battery negative material is still current
Hot spot.
At present, in the research of lithium ion battery negative material, the research of Carbon materials is still a hot spot, mainly
It is to concentrate on (reference in terms of graphene：1st, the Huanghai Sea is put down, and Zhu person of outstanding talent carbon materials-graphene is prepared and its in electrochemistry
Using [J] analytical chemistry, 2011,39 (7):963-971；2、Guo H.-L.,Wang X.-F.,Qian Q.-Y.,et al.A
green approach to the synthesis of graphene nanosheets[J].ACS nano,2009,3(9):
2653-2659；3、Wang Z.-L.,Xu D.,Wang H.-G.,et al.In situ fabrication of porous
graphene electrodes for high performance energy storage[J].ACS nano,2013,7
(3):2422-2430), it but is still has no idea to prepare graphene on a large scale at present, the research for graphene is also
It is only limitted to the experimental stage.So promote to prepare also just being particularly important for other kinds of porous carbon materials.Wherein utilize
It is exactly a selection well that metal organic framework compound, which prepares porous carbon materials,.Metal organic framework compound (MOFs) is made
For a kind of porous solid material, there is completely regular structure, the porosity and specific surface area of superelevation, and synthetic method temperature
Abundant (different organic ligands can form different structures) with the selection of, raw material, these features make it have other materials
Incomparable advantage, and heterogeneous catalysis, gas storage with detaching, the fields such as optics, magnetism are with important application.It is but near
By metal organic framework compound for the research (reference in terms of clean energy resource over year：Li S L,Xu Q.Metal–organic
frameworks as platforms for clean energy[J].Energy&Environmental Science,
2013,6(6):Although 1656-1683.) few, trend is good, and development space is very big.Since Xu in 2010
Qiang (references：Jiang H L,Liu B,Lan Y Q,et al.From metal–organic framework to
nanoporous carbon:toward a very high surface area and hydrogen uptake[J]
.Journal of the American Chemical Society,2011,133(31):11854-11857.) seminar head
The secondary porous carbon materials prepared using metal organic framework compound are started for the research of ultracapacitor, people begin to by
Gradually pay close attention to this method (reference for preparing carbon material：1、Zheng F,Yang Y,Chen Q.High lithium anodic
performance of highly nitrogen-doped porous carbon prepared from a metal-
organic framework[J].Nature communications,2014,5；2、Zuo L,Chen S,Wu J,et
al.Facile synthesis of three-dimensional porous carbon with high surface area
by calcining metal–organic framework for lithium-ion batteries anode
materials[J].RSC Advances,2014,4(106):61604-61610.)。
In the present invention, MOFs (metal organic framework compound)：A kind of organic-inorganic hybrid material, by organic ligand with
Inorganic metal cell formation forms.
ZIF (imidazoles zeolites organic frame compound)：Belong to a branch of metal organic framework compound, it is organic
Ligand is mainly imidazoles and imidazoles analog, and one kind of formation is similar to zeolite structured frame chemical combination with porous structure
Object.
Self-discharge phenomenon：Refer to accumulator in the case of idle, can also consume electricity, this phenomenon is known as oneself of accumulator
Electric discharge phenomena.Main cause is that irreversible reaction has occurred in inside battery, so as to cause the loss of battery capacity.
Li dendrite：Refer to the lithium battery using liquid electrolyte in charging, lithium ion restores the dendritic metal to be formed
The phenomenon that lithium simple substance.
Specific capacity：It is divided into weight ratio capacity and volume and capacity ratio, more is that (unit is mAh/ to weight ratio capacity
G), refer to the electricity that the battery of Unit Weight or active material can release.It is an important symbol for weighing battery performance quality.
High rate performance：Charge and discharge, electricity are carried out to battery under different current densities (such as 100mA/g, 1000mA/g)
(ratio) amount of capacity and an important symbol of measurement battery performance quality that pond is showed, generally can be with charge and discharge electricity
The raising of current density, specific capacity can decline.
Cycle performance is tested：Refer to and charge and discharge are carried out to battery under a certain current density, see charge and discharge number to specific capacity
Influence.
Constant current charge-discharge test：It is the parameters such as the specific capacity height for examining rechargeable battery, multiplying power property, cycle performance
Important means.
Invention content
Goal of the invention：In order to solve the deficiencies in the prior art, the present invention provides a kind of lithium ions based on ZIF complexs
The preparation method of cell negative electrode material.
Technical solution：A kind of preparation method of the lithium ion battery negative material based on ZIF complexs, including walking as follows
Suddenly：
Step 1：Take ZnNO3·6H2O, 2-methylimidazole, 2,3- three kinds of pyridinedicarboxylic acid reactants add the water to be in liner
In the reaction kettle of polytetrafluoroethylene (PTFE) material, three kinds of reactant ZnNO3·6H2O, 2-methylimidazole, 2,3- pyridinedicarboxylic acids
Ratio is 1:1:1, it is described plus water be liner capacity 1/4-3/4, at a certain temperature in the range of 100 DEG C -160 DEG C, instead
Answer two days, after decrease speed using temperature as 1 DEG C/10min be down to room temperature；
Step 2：Take in step 1 that crystal on sheet glass, selects suitable crystal under the microscope in reaction kettle,
It is measured on " Bruker APEX-II CCD " type monocrystalline instrument, obtains crystal data, using software APEXII softwares into line number
According to analysis, crystal structure is parsed, chemical formula is [Zn6(2-MIm)10·2H2O], it carries out structure chart using Diamond softwares and paints
System；
Step 3：According to the method in step 1, presoma is largely synthesized, is cooled to room temperature, is filtered to obtain a large amount of
Pale yellow crystals；
Step 4：The a large amount of crystal powder namely presoma that step 3 is obtained, in inert atmosphere：Nitrogen or argon gas
Lower calcining, calcination temperature range are between 700 DEG C -900 DEG C, after reaching target temperature with the heating rate of 5 DEG C/min, in target
At a temperature of stop 8h, after allow its natural cooling；
Step 5：The black solid powder obtained in step 4 is subjected to immersion 36h with 30% hydrofluoric acid solution, during which
It replaces hydrofluoric acid solution twice and is stirred continuously, washed later with a large amount of water, until solution is in neutrality；
Step 6：The solid powder that step 5 obtains is dried, and is applied to negative electrode of lithium ion battery material
In material；
Step 7：The material obtained in step 6 is subjected to dicing, lithium ion battery negative electrode is made；
Step 8：Electrochemical property test：Voltage range in constant current charge-discharge test is 0.01V-3.0V, cycle performance
Charge-discharge test number is 100 times during test, and current density is 100mA/g, has been respectively adopted in high rate performance test
Constant current charge-discharge is carried out under 100mA/g, 200mA/g, 500mA/g, 1000mA/g, and cycle-index is 10 under each multiplying power
It is secondary.
As advanced optimizing：The concrete operations of the step 6 are as follows：By cell negative electrode material and Kynoar
(PVDF), conductive acetylene is black with mass ratio 8:1:1 ground and mixed is uniform, is slurred with N-Methyl pyrrolidone (NMP) for solvent
Shape is coated on copper foil, first the dry 1h in 80 DEG C of baking oven, then 120 DEG C of dry 10h in vacuum drying chamber.
As advanced optimizing：The concrete operations of the step 7 are as follows：Using lithium piece as to electrode, PE (polyethylene) be every
Membrane material, using the LiPF containing 1mol/L6For electrolyte, volume ratio EC:DEC:EMC=1:1:1 electrolyte for solvent, LiPF6
It is lithium hexafluoro phosphate, it be methyl ethyl carbonate, DEC is diethyl carbonate that EC, which is ethylene carbonate, EMC, and button cell model is
2025, carry out composition button cell.
As advanced optimizing：In the step 1,0.1mmol ZnNO are taken3·6H2O, 0.1mmol 2-MIm (2- methyl
Imidazoles), 0.1mmol 2,3- pyridinedicarboxylic acids, 5ml water is in the reaction kettle of polytetrafluoroethylene (PTFE) material in the liner of 15ml.
Advantageous effect：The specific advantage of the present invention is as follows：
(1) present invention prepares the porous of nitrating by synthesizing a kind of imidazoles zeolites organic frame compound using it
Carbon material, and be applied in the negative material of lithium ion battery, first discharge specific capacity can be reached for 1211mAh/g,
When charging and discharging currents density is 100mA/g, specific capacity is nearly all in 620mAh/g or so (and commercialized graphite cathode ratios
Capacity Theory value is 372mAh/g), even after recycling 100 times, its good cycle performance is embodied, and in current density
When being 1000mA/g, specific capacity can also reach 410mAh/g, embody its good high rate performance.
(2) commercial Li-ion battery negative material is all to use graphite type material at present, but its theoretical capacity only has
372mAh/g largely limits development of the lithium ion battery to electrical equipment.And the present invention is born for existing lithium battery
The shortcomings that pole material, the present invention prepare the porous carbon materials of nitrating to obtain by the use of metal organic framework compound as presoma
Negative material with high specific capacity.
(3) in the present invention, negative material structure, specific surface area are adjustable, and negative material chemical property easy to implement carries
It is high.Since the structure and specific surface area of presoma metal organic framework compound are adjustable, by select different calcination temperatures come
Realize the regulation and control of the structure of porous carbon materials that calcining is prepared.The structure unicity of existing graphitic carbon material is avoided,
And then easily optimize and obtain high performance lithium cell cathode material.
(4) it in the present invention, by the use of the fixed nitrogen heterocyclic ring frame complex of even structure as presoma, fully ensures that and forges
The uniformity of lithium cell negative pole material nitrogen doped being prepared after burning.The specific capacity of negative material in this way is improved same
When, cyclical stability is also guaranteed.
Description of the drawings
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 complex [Zn obtained in the embodiment of the present invention 16(2-MIm)10·2H2O] XRD diagram；
Fig. 4 is the XRD diagram of the carbon material of the N doping obtained in the embodiment of the present invention 1；
Fig. 5 is the EDS figures of the carbon material of the N doping obtained in the embodiment of the present invention 1；
Fig. 6 is the SEM figures of the carbon material of the N doping obtained in the embodiment of the present invention 1；
Fig. 7 is the TEM figures of the carbon material of the N doping obtained in the embodiment of the present invention 1；
Fig. 8 is the cycle performance test chart of the negative material obtained in the embodiment of the present invention 1；
Fig. 9 is the high rate performance test chart of the negative material obtained in the embodiment of the present invention 1；
Figure 10 is the constant current charge-discharge curve test chart of the negative material obtained in the embodiment of the present invention 1.
Specific embodiment
With reference to specific embodiment, the invention will be further described.
Specific embodiment 1：
(1) preparation of negative material (carbon material of N doping)
Step 1：Take 0.1mmol ZnNO3·6H2O, 0.1mmol 2-methylimidazole, 0.1mmol 2,3- pyridine dicarboxyls
Acid, 5ml water is in reaction kettle of the liner for polytetrafluoroethylene (PTFE) material of 15ml, after being reacted 2 days at 100-160 DEG C of temperature range
Decrease speed using temperature as 1 DEG C/10min is down to room temperature.
Step 2：Take in step 1 that crystal on sheet glass, selects suitable crystal under the microscope in reaction kettle, "
It is measured on Bruker APEX-II CCD " type monocrystalline instrument, obtains crystal data, data are carried out using software APEXII softwares
Analysis, solves crystal structure, it is [Zn to solve crystal-chemical formula6(2-MIm)10·2H2O], carry out structure using Diamond softwares
Figure is drawn.Fig. 1:For the tomograph that Diamond softwares is utilized to draw after APEXII softwares solve crystal structure.Fig. 2:For
The three-dimensional topology figure drawn after APEXII softwares solve crystal structure using Diamond softwares.
Step 3：According to the method in step 1, presoma is largely synthesized, is cooled to room temperature, is filtered to obtain a large amount of
Pale yellow crystals.Fig. 3:It is a large amount of sample X-ray diffractograms after the operation of step 3, illustrates a large amount of sample of synthesis
Diffraction pattern and the X-ray diffractogram of sample by simulation be consistent.
Step 4：By a large amount of crystal powder (namely presoma) that step 3 obtains in inert atmosphere (nitrogen or argon gas)
Lower calcining, calcination temperature range are 700-900 DEG C, after reaching target temperature with the heating rate of 5 DEG C/min, under target temperature
Stop 8h, after allow its natural cooling.
Step 5：The black solid powder obtained in step 4 is subjected to immersion 36h with 30% hydrofluoric acid solution, during which
It replaces hydrofluoric acid solution twice and is stirred continuously, washed later with a large amount of water, until solution is in neutrality.After drying i.e.
It can obtain the carbon material of N doping.Fig. 4:It is that X-ray diffraction analysis is carried out to the obtained carbon material of N doping, it can be seen that
23 ° there are one wide diffraction maximums, are the characteristic peak of carbon.Also demonstrate that the material prepared in the present invention belongs to the scope of carbon material.
Fig. 5:It is the scanning electron microscope (SEM) photograph of the carbon material of the N doping obtained after step 5 operates, it can be seen that material is to belong to micron
Rank.Fig. 6:It is the Flied emission transmission electron microscope picture of the carbon material of the N doping obtained after step 5 operates, it can be seen that
Particle dispersion is almost uniform.Fig. 7:It is the EDS figures of the nitrogen-doped carbon material obtained after step 5 operates, it can be seen that
Metallic zinc has not been contained in sample after treatment, has illustrated that metallic zinc has been fully processed totally, adequately confirms
The material of preparation is the carbon material of N doping.
(2) preparation of electrode
The solid powder that step 5 obtains is dried, and is applied in lithium ion battery negative material.
I.e.：Cell negative electrode material and Kynoar (PVDF), conductive acetylene is black with mass ratio 8:1:1 ground and mixed is uniform, with N-
Methyl pyrrolidone (NMP) is tuned into pulpous state for solvent, is coated on copper foil, and first the dry 1h in 80 DEG C of baking oven, then exists
120 DEG C of dry 10h in vacuum drying chamber.Piece is then cut into, lithium ion battery negative electrode is made.Using lithium piece as to electrode,
PE (polyethylene) is diaphragm material, and button cell model is 2025, carries out composition button cell, then carries out chemical property survey
Examination.
(3) electrode performance is tested
Temperature is room temperature during test, and the voltage range in constant current charge-discharge test is 0.01V-3.0V, cycle performance test
When charge-discharge test number be 100 times, current density is 100mA/g, has been respectively adopted in high rate performance test in 100mA/g,
Constant current charge-discharge is carried out under 200mA/g, 500mA/g, 1000mA/g, and cycle-index is 10 times under each multiplying power.Fig. 8 be
When current density is 100mA/g, voltage range is that 0.01-3.0V carries out specific capacity-cycle-index figure that constant current charge-discharge obtains,
Even it can be seen from the figure that cycle 100 times after specific capacity can also maintain 620mAh/g or so, substantially without
What attenuation, illustrates that the material synthesized in the present invention is good as lithium ion battery negative material cycle performance.Fig. 9 is in electric current
Density is 100mA/g, 200mA/g, 500mA/g respectively, and carrying out constant current charge-discharge test under 1000mA/g obtains high rate performance figure,
And cycle-index is 10 times under each multiplying power, and the material high rate performance as can be seen from the figure synthesized in the present invention is good.Figure
10 be when current density is 100mA/g, and voltage range is that 0.01-3.0V carries out voltage-specific capacity that constant current charge-discharge obtains
Figure, as can be seen from the figure initial discharge specific capacity can reach 1211mAh/g, and discharge platform mainly concentrates on 0.5V
Hereinafter, this meets the flash-over characteristic of common carbon material.
Specific embodiment 2
A kind of preparation method of the lithium ion battery negative material based on ZIF complexs, includes the following steps：
Step 1：Take ZnNO3·6H2O, 2-methylimidazole, 2,3- three kinds of pyridinedicarboxylic acid reactants add the water to be in liner
In the reaction kettle of polytetrafluoroethylene (PTFE) material, three kinds of reactant ZnNO3·6H2O, the ratio of 2-MIm, 2,3- pyridinedicarboxylic acid
It is 1:1:1, it is described plus water be liner capacity 1/4, at a temperature of 100 DEG C, react two days, after using temperature as 1 DEG C/
The decrease speed of 10min is down to room temperature.
Step 2：Take in step 1 that crystal on sheet glass, selects suitable crystal under the microscope in reaction kettle,
It is measured on " Bruker APEX-II CCD " type monocrystalline instrument, obtains crystal data, using software APEXII softwares into line number
According to analysis, crystal structure is parsed, chemical formula is [Zn6(2-MIm)10·2H2O], it carries out structure chart using Diamond softwares and paints
System.
Step 3：According to the method in step 1, presoma is largely synthesized, is cooled to room temperature, is filtered to obtain a large amount of
Pale yellow crystals.
Step 4：The a large amount of crystal powder namely presoma that step 3 is obtained, in inert atmosphere：Nitrogen or argon gas
Lower calcining, calcination temperature is 700 DEG C, and after reaching target temperature with the heating rate of 5 DEG C/min, 8h is stopped under target temperature,
After allow its natural cooling.
Step 5：The black solid powder obtained in step 4 is subjected to immersion 36h with 30% hydrofluoric acid solution, during which
It replaces hydrofluoric acid solution twice and is stirred continuously, washed later with a large amount of water, until solution is in neutrality.
Step 6：The solid powder that step 5 obtains is dried, and is applied to negative electrode of lithium ion battery material
In material, concrete operations are as follows：Cell negative electrode material and Kynoar (PVDF), conductive acetylene is black with mass ratio 8:1:1 grinds
Mill is uniformly mixed, and is tuned into pulpous state for solvent with N-Methyl pyrrolidone (NMP), is coated on copper foil, first in 80 DEG C of baking oven
Middle dry 1h, then 120 DEG C of dry 10h in vacuum drying chamber.
Step 7：The material obtained in step 6 is subjected to dicing, lithium ion battery negative electrode is made, it is specific to grasp
Make as follows：Using lithium piece as to electrode, PE (polyethylene) is diaphragm material, using the LiPF containing 1mol/L6For electrolyte, volume ratio
EC:DEC:EMC=1:1:1 electrolyte for solvent, LiPF6It is lithium hexafluoro phosphate, it is carbonic acid first that EC, which is ethylene carbonate, EMC,
Ethyl ester, DEC are diethyl carbonates, and button cell model is 2025, carries out composition button cell.
Step 8：Electrochemical property test：Voltage range in constant current charge-discharge test is 0.01V, and cycle performance is tested
When charge-discharge test number be 100 times, current density is 100mA/g, has been respectively adopted in high rate performance test in 100mA/g,
Constant current charge-discharge is carried out under 200mA/g, 500mA/g, 1000mA/g, and cycle-index is 10 times under each multiplying power.
Specific embodiment 3
A kind of preparation method of the lithium ion battery negative material based on ZIF complexs, includes the following steps：
Step 1：Take ZnNO3·6H2O, 2-methylimidazole, 2,3- three kinds of pyridinedicarboxylic acid reactants add the water to be in liner
In the reaction kettle of polytetrafluoroethylene (PTFE) material, three kinds of reactant ZnNO3·6H2O, the ratio of 2-MIm, 2,3- pyridinedicarboxylic acid
It is 1:1:1, it is described plus water be liner capacity 3/4, at a temperature of 160 DEG C, react two days, after using temperature as 1 DEG C/
The decrease speed of 10min is down to room temperature.
Step 2：Take in step 1 that crystal on sheet glass, selects suitable crystal under the microscope in reaction kettle,
It is measured on " Bruker APEX-II CCD " type monocrystalline instrument, obtains crystal data, using software APEXII softwares into line number
According to analysis, crystal structure is parsed, chemical formula is [Zn6(2-MIm)10·2H2O], it carries out structure chart using Diamond softwares and paints
System.
Step 3：According to the method in step 1, presoma is largely synthesized, is cooled to room temperature, is filtered to obtain a large amount of
Pale yellow crystals.
Step 4：The a large amount of crystal powder namely presoma that step 3 is obtained, in inert atmosphere：Nitrogen or argon gas
Lower calcining, calcination temperature range are between 900 DEG C, after reaching target temperature with the heating rate of 5 DEG C/min, under target temperature
Stop 8h, after allow its natural cooling.
Step 5：The black solid powder obtained in step 4 is subjected to immersion 36h with 30% hydrofluoric acid solution, during which
It replaces hydrofluoric acid solution twice and is stirred continuously, washed later with a large amount of water, until solution is in neutrality.
Step 6：The solid powder that step 5 obtains is dried, and is applied to negative electrode of lithium ion battery material
In material, concrete operations are as follows：Cell negative electrode material and Kynoar (PVDF), conductive acetylene is black with mass ratio 8:1:1 grinds
Mill is uniformly mixed, and is tuned into pulpous state for solvent with N-Methyl pyrrolidone (NMP), is coated on copper foil, first in 80 DEG C of baking oven
Middle dry 1h, then 120 DEG C of dry 10h in vacuum drying chamber.
Step 7：The material obtained in step 6 is subjected to dicing, lithium ion battery negative electrode is made, it is specific to grasp
Make as follows：Using lithium piece as to electrode, PE (polyethylene) is diaphragm material, using the LiPF containing 1mol/L6For electrolyte, volume ratio
EC:DEC:EMC=1:1:1 electrolyte for solvent, LiPF6It is lithium hexafluoro phosphate, it is carbonic acid first that EC, which is ethylene carbonate, EMC,
Ethyl ester, DEC are diethyl carbonates, and button cell model is 2025, carries out composition button cell.
Step 8：Electrochemical property test：Voltage range in constant current charge-discharge test is 3.0V, when cycle performance is tested
Charge-discharge test number is 100 times, and current density is 100mA/g, has been respectively adopted in high rate performance test in 100mA/g,
Constant current charge-discharge is carried out under 200mA/g, 500mA/g, 1000mA/g, and cycle-index is 10 times under each multiplying power.
Specific embodiment 4
A kind of preparation method of the lithium ion battery negative material based on ZIF complexs, includes the following steps：
Step 1：Take ZnNO3·6H2O, 2-methylimidazole, 2,3- three kinds of pyridinedicarboxylic acid reactants add the water to be in liner
In the reaction kettle of polytetrafluoroethylene (PTFE) material, three kinds of reactant ZnNO3·6H2O, the ratio of 2-MIm, 2,3- pyridinedicarboxylic acid
It is 1:1:1, it is described plus water be liner capacity 1/2, at a temperature of 130 DEG C, react two days, after using temperature as 1 DEG C/
The decrease speed of 10min is down to room temperature.
Step 2：Take in step 1 that crystal on sheet glass, selects suitable crystal under the microscope in reaction kettle,
It is measured on " Bruker APEX-II CCD " type monocrystalline instrument, obtains crystal data, using software APEXII softwares into line number
According to analysis, crystal structure is parsed, chemical formula is [Zn6(2-MIm)10·2H2O], it carries out structure chart using Diamond softwares and paints
System.
Step 3：According to the method in step 1, presoma is largely synthesized, is cooled to room temperature, is filtered to obtain a large amount of
Pale yellow crystals.
Step 4：The a large amount of crystal powder namely presoma that step 3 is obtained, in inert atmosphere：Nitrogen or argon gas
Lower calcining, calcination temperature range are between 800 DEG C, after reaching target temperature with the heating rate of 5 DEG C/min, under target temperature
Stop 8h, after allow its natural cooling.
Step 5：The black solid powder obtained in step 4 is subjected to immersion 36h with 30% hydrofluoric acid solution, during which
It replaces hydrofluoric acid solution twice and is stirred continuously, washed later with a large amount of water, until solution is in neutrality.
Step 6：The solid powder that step 5 obtains is dried, and is applied to negative electrode of lithium ion battery material
In material, concrete operations are as follows：Cell negative electrode material and Kynoar (PVDF), conductive acetylene is black with mass ratio 8:1:1 grinds
Mill is uniformly mixed, and is tuned into pulpous state for solvent with N-Methyl pyrrolidone (NMP), is coated on copper foil, first in 80 DEG C of baking oven
Middle dry 1h, then 120 DEG C of dry 10h in vacuum drying chamber.
Step 7：The material obtained in step 6 is subjected to dicing, lithium ion battery negative electrode is made, it is specific to grasp
Make as follows：Using lithium piece as to electrode, PE (polyethylene) is diaphragm material, using the LiPF containing 1mol/L6For electrolyte, volume ratio
EC:DEC:EMC=1:1:1 electrolyte for solvent, LiPF6It is lithium hexafluoro phosphate, it is carbonic acid first that EC, which is ethylene carbonate, EMC,
Ethyl ester, DEC are diethyl carbonates, and button cell model is 2025, carries out composition button cell.
Step 8：Electrochemical property test：Voltage range in constant current charge-discharge test is 2.0V, when cycle performance is tested
Charge-discharge test number is 100 times, and current density is 100mA/g, has been respectively adopted in high rate performance test in 100mA/g,
Constant current charge-discharge is carried out under 200mA/g, 500mA/g, 1000mA/g, and cycle-index is 10 times under each multiplying power.
The present invention is not limited to above-mentioned preferred forms, anyone can show that other are various under the enlightenment of the present invention
The product of form, however, make any variation in its shape or structure, it is every that there is skill identical or similar to the present application
Art scheme, is within the scope of the present invention.
Claims (4)
1. a kind of preparation method of the lithium ion battery negative material based on ZIF complexs, it is characterised in that：Including walking as follows
Suddenly：
Step 1：Take ZnNO3·6H2O, 2-methylimidazole, 2,3- three kinds of pyridinedicarboxylic acid reactants, add water in liner be poly- four
In the reaction kettle of vinyl fluoride material, three kinds of reactant ZnNO3·6H2O, the ratio of 2-methylimidazole, 2,3- pyridinedicarboxylic acids
It is 1:1:1, it is described plus water be liner capacity 1/4-3/4, at a certain temperature in the range of 100 DEG C -160 DEG C, reaction two
My god, after decrease speed using temperature as 1 DEG C/10min be down to room temperature；
Step 2：Take in step 1 that crystal on sheet glass, selects suitable crystal under the microscope in reaction kettle,
It is measured on " Bruker APEX-II CCD " type monocrystalline instrument, obtains crystal data, using software APEXII softwares into line number
According to analysis, crystal structure is parsed, chemical formula is [Zn6(2-MIm)10·2H2O], it carries out structure chart using Diamond softwares and paints
System；
Step 3：According to the method in step 1, presoma is largely synthesized, is cooled to room temperature, is filtered to obtain a large amount of pale yellow
Color crystal；
Step 4：The a large amount of crystal powder namely presoma that step 3 is obtained, are forged under inert atmosphere nitrogen or argon gas
It burns, calcination temperature range is between 700 DEG C -900 DEG C, after reaching target temperature with the heating rate of 5 DEG C/min, in target temperature
Lower stop 8h, after allow its natural cooling；
Step 5：The black solid powder obtained in step 4 is subjected to immersion 36h with 30% hydrofluoric acid solution, is during which replaced
Hydrofluoric acid solution twice and is stirred continuously, and is washed later with a large amount of water, until solution is in neutrality；
Step 6：The solid powder that step 5 obtains is dried, and is applied in lithium ion battery negative material；
Step 7：The material obtained in step 6 is subjected to dicing, lithium ion battery negative electrode is made；
Step 8：Electrochemical property test：Voltage range in constant current charge-discharge test is 0.01V-3.0V, and cycle performance is tested
When charge-discharge test number be 100 times, current density is 100mA/g, has been respectively adopted in high rate performance test in 100mA/g,
Constant current charge-discharge is carried out under 200mA/g, 500mA/g, 1000mA/g, and cycle-index is 10 times under each multiplying power.
2. the preparation method of the lithium ion battery negative material according to claim 1 based on ZIF complexs, feature exist
In：The concrete operations of the step 6 are as follows：Cell negative electrode material and Kynoar (PVDF), conductive acetylene is black with quality
Than 8:1:1 ground and mixed is uniform, is tuned into pulpous state for solvent with N-Methyl pyrrolidone (NMP), is coated on copper foil, first 80
DEG C baking oven in dry 1h, then 120 DEG C of dry 10h in vacuum drying chamber.
3. the preparation method of the lithium ion battery negative material according to claim 1 based on ZIF complexs, feature exist
In：The concrete operations of the step 7 are as follows：Using lithium piece as to electrode, PE (polyethylene) is diaphragm material, using containing 1mol/L
LiPF6For electrolyte, volume ratio EC:DEC:EMC=1:1:1 electrolyte for solvent, LiPF6It is lithium hexafluoro phosphate, EC is carbon
Vinyl acetate, EMC are that methyl ethyl carbonate, DEC are diethyl carbonates, and button cell model is 2025, carries out composition button cell.
4. the preparation method of the lithium ion battery negative material according to claim 1 based on ZIF complexs, feature exist
In：In the step 1,0.1mmol ZnNO are taken3·6H2O, 0.1mmol 2-methylimidazole, 0.1mmol 2,3- pyridine dicarboxyls
Acid, 5ml water are in the reaction kettle of polytetrafluoroethylene (PTFE) material in the liner of 15ml.
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| CN110894298B (en) * | 2018-09-13 | 2022-03-22 | 北京大学深圳研究生院 | Preparation method of MOFs nano material and derivative thereof |
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