CN108615891A - A kind of preparation method of zinc-base complex lithium ion battery negative material - Google Patents
A kind of preparation method of zinc-base complex lithium ion battery negative material Download PDFInfo
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Abstract
Zinc nitrate, [chlorination 1,1 ' two (3 carboxyl benzylidene) 4,4 ' bipyridyls], terephthalic acid (TPA), ammonium hexafluorophosphate and distilled water are added to by a kind of zinc-base complex lithium ion battery negative material preparation method（N, N dimethylformamide）In, it stirs evenly at room temperature.Mixing liquid is moved on in Teflon autoclave again, is heated to 120 C constant temperature, 24 h.To be down to room temperature after reaction, white needle-like crystals are obtained.Be filtered, washed, dry after obtain the complex Zn bPTA.This material, first discharge specific capacity reach 816.3mAh/g；2nd time cycle specific discharge capacity be 407.5mAh/g, 100 times cycle after discharge capacity 386.2mAh/g.Equipment requirement is low, easy to operate.The zinc-base complex material stable structure of synthesis, it is cheap, it is environmental-friendly, it is a kind of lithium ion battery negative material of structure novel.
Description
Technical field
The present invention relates to a kind of preparation methods of zinc-base complex lithium ion battery negative material.This material abbreviation Zn-
BPTA has preferable chemical property and good cyclical stability.
Background technology
Current lithium ion battery is widely used to the fields such as portable electronic device, new-energy automobile, energy storage base station, not
The application for carrying out lithium ion battery can be more universal.However lithium ion battery is developed so far, energy density is still reached to less than people
Demand, this is mainly limited by the performance of lithium ion battery electrode material.The electrode material system of traditional lithium ion battery
Based on inorganic material, such as layer structure type LiCoO2And its derivative, polyanionic LiFePO4And its derivative, point are brilliant
Stone-type LiMn2O4And its derivative.For negative material mainly based on carbon material, other negative materials further include Si bases cathode, Sn bases
Cathode, Li4Ti5O12Deng.These positive and negative pole materials have respective apparent advantage and disadvantage.Most its performance of business electrode material
It is promoted to vertex, to further increase the energy density of lithium ion battery, future there is still a need for the research to deepen continuously, opens
Send out the electrode material of new system.Metal complex not only has the structural stability of inorganic material, while also having had both organic material
Expect structure-rich, novelty, it is controllable the advantages that, have extraordinary research and development potentiality.Therefore, complex material is recognized as future
It is possible to be widely used in lithium ion battery.Complex electrode synthesis step is simple, at low cost, and can have in performance non-
Often good oxidation-reduction pair, electrochemical window are controllable.Simultaneously complex structure it is very flexible and changeable, can be large scale from
Son（102 pm）Improve the migrating channels of number of ways.Therefore the complex with oxidation-reduction pair in structure, can use extensively
Make lithium ion battery electrode material, has a good application prospect.
Recently more and more researchers change electrode system from purely inorganic to metal complex, but obtain big
Capacity, high circulation stability complex electrode material still have many difficulties.
Invention content
The object of the present invention is to provide a kind of preparation method of zinc-base complex lithium ion battery negative material, with solve by
Electrode system is from the purely inorganic conversion techniques to metal complex, the existing cooperation that obtain large capacity, high circulation stability
The difficult problem that object electrode material still has.
Technical solution：
A kind of preparation method of zinc-base complex lithium ion battery negative material, including prepared by zinc-base complex, electrode slurry system
It is standby, electrode slurry is dry and is assembled into button cell technique；Specific steps include as follows：
（1）Zn(NO3)2·6H2O（Zinc nitrate）、H2Bcbpy2Cl [chlorination -1,1 '-two (3- carboxyls-benzylidene) -4,
4 '-bipyridyls], HOOCC6H4COOH（Terephthalic acid (TPA)）、NH4PF6（Ammonium hexafluorophosphate）According to molar ratio 2:1:2:2 ratio,
It is added to distilled water and DMF（N, N- dimethylformamide）Mixed solution（Volume ratio 1:1）In, it is stirred under air at room temperature atmosphere
30min。
（2）By step（1）Mixture after middle stirring is transferred in the Teflon autoclave of 25mL, and 110~130
℃；Step（2）The middle reaction time be 20~for 24 hours, be cooled to room temperature after reaction with the rate of temperature fall of 10 DEG C/h, obtain white
Acicular crystal.
（3）By step（2）In obtain white needle-like crystals and be washed with distilled water, filter 2 times, the vacuum at 80~100 DEG C
Dry 10~12h, obtains zinc-base complex Zn-bPTA.
（4）By step（3）In obtain zinc-base complex Zn-bPTA, PVDF（Kynoar）、KS6（Electrically conductive graphite）、
Super-P（Super carbon black）According to mass ratio 60:10:20:10 or 50:10:20:20 configuration resulting mixtures, in mass ratio 1:
2.5-4 solvent NMP is added（N-Methyl pyrrolidone）In, the electrode slurry of dark thick is prepared into after stirring 2h.
（5）By step（4）In obtained dark thick electrode slurry, be coated on metal copper foil, coating thickness is 20 μm
~50 μm, coated electrode is first with after 120 DEG C of forced air drying 3h, then dry 6~12h under 100 DEG C of vacuum, obtain preparing lithium from
The electrode of sub- battery.
（6）By step（5）In obtained battery electrode be cut into the round pole piece of a diameter of 14mm, the metal of a diameter of 14mm
Lithium piece is used as to electrode, and electrolyte is：1mol/L LiPF6It is dissolved in ethylene carbonate（EC）And dimethyl carbonate（DMC）It is molten
In agent（Molar ratio EC：DMC=1:1）, in the glove box full of argon gas, it is assembled into 2025 type button cells.
Zn (the NO3)2·6H2O、H2bcbpy·2Cl、HOOCC6H4COOH、NH4PF6, it is that analysis is pure.
Zn (the NO3)2·6H21~4mmol is added according to the volume of reaction kettle in O；H2Bcbpy2Cl is according to reaction kettle
Volume be added 0.5~2mmol；HOOCC6H41~4mmol is added according to the volume of reaction kettle in COOH；NH4PF6According to reaction kettle
Volume be added 1~4mmol；Teflon reaction kettle volume is 25~100mL.
Zn (the NO3)2·6H2O、 H2bcbpy·2Cl、HOOCC6H4COOH、NH4PF6Ratio according to molar ratio 2:1:
2:2 progress are mixed uniformly.
The solvent is distilled water and DMF mixed solutions, volume ratio 1:1, the addition in the reaction kettle that volume is adapted
For 25~100mL.
The step（1）In mixing time be 30~60min, stir speed (S.S.) be 500~800 r/min.
The step（2）In reaction temperature be 120 DEG C, the reaction time for 24 hours, after reaction with the cooling of 10 DEG C/h speed
Rate is cooled to room temperature.
The step（3）In it is washed after filter, be dried in vacuo 12h at 80 DEG C.
The step（4）Middle complex Zn-bPTA, PVDF, KS6, Super-P are according to mass ratio 60:10:20:10 or 50:
10:20:20；The amount that NMP is added is 2.5 times of mixture Zn-bPTA, PVDF, KS6, Super-P total weight.
The step（5）Middle electrode slurry coating thickness is the thickness of any concrete numerical value in 20~50 μm.At 120 DEG C
Forced air drying 3h, then 100 DEG C of vacuum drying 9h.
Described PVDF, KS6, Super-P are LITHIUM BATTERY.
The electrolyte is：1mol/L LiPF6It is dissolved in ethylene carbonate（EC）And dimethyl carbonate（DMC）Solvent
In（Molar ratio EC：DMC=1:1）.
The step（2）Middle reaction temperature be 110~130 DEG C between any actual temp value, the reaction time be 20~for 24 hours
Between adaptation time value, cooling rate be 10 DEG C/h.
The step（3）Middle washing times are 2-3 times.
The step（3）In vacuum drying temperature be 80~100 DEG C between any actual temp value, drying time 10~
12h。
The step（4）Middle mixing time is 2-3h.
Compared with the prior art, the advantages of the present invention are as follows：A kind of complex lithium ion battery negative material（Abbreviation Zn-
bPTA）.There is the metal complex Zn-bPTA structure novel, structure to report having for the first time applied to lithium ion cell electrode for the first time
In material.The Zn-bPTA metal complex materials, at 0.01V-3V, the current density of 100 mA/g, first discharge specific capacity
Reach 816.3 mAh/g；2nd time cycle specific discharge capacity be 407.5 mAh/g, 100 times cycle after discharge capacity 386.2
mAh/g.The present invention is low to synthesis device requirement, simple to operate.Synthesized novel zinc-base complex Zn-bPTA materials
Stable structure, it is cheap, it is environmental-friendly, it is a kind of lithium ion battery negative material of structure novel.
Description of the drawings
Fig. 1 is the XRD spectrum of 1 product of the embodiment of the present invention；
Fig. 2 is the SEM+EDX collection of illustrative plates of 1 product of the embodiment of the present invention；
Fig. 3 is the CV curves of 1 product of the embodiment of the present invention；
Fig. 4 is the charging and discharging curve of 1 product of the embodiment of the present invention；
Fig. 5 is 100 cyclic curves of 1 product of the embodiment of the present invention；
Fig. 6 is the XRD spectrum of 2 product of the embodiment of the present invention；
Fig. 7 is the SEM+EDX collection of illustrative plates of 2 product of the embodiment of the present invention；
Fig. 8 is the CV curves of 2 product of the embodiment of the present invention；
Fig. 9 is the charging and discharging curve of 2 product of the embodiment of the present invention；
Figure 10 is 100 cyclic curves of 2 product of the embodiment of the present invention.
Figure 11 is the crystal structure figure of Zn-bPTA complexs.
Specific implementation mode
The present invention is further described for following embodiment combination Figure of description.
Embodiment 1：By Zn (NO3)2·6H2O (1.0 mmol, 297 mg)、H2bcbpy·2Cl (0.5 mmol,
258 mg)、HOOCC6H4COOH(1.0 mmol, 166 mg)、NH4PF6(1.0 mmol, 163 mg) are mixed, and are added to distillation
In the mixed solution of water (8 mL) and DMF (8 mL), 30min is stirred under air at room temperature atmosphere.Then mixing liquid is shifted
Into 25ml Teflon autoclaves, it is heated to 120 C constant temperature, 24 h.It is cooled to after reaction with the rate of 10 C/h
Room temperature obtains white needle-like crystals, be filtered, washed, dry after obtain the complex Zn-bPTA, calculation of yield is about
83%.It will obtain the ground 300 mesh sieve of Zn-bPTA electrode materials.By metal complex Zn-bPTA（0.6g）、PVDF（0.1g）、
KS6（0.2g）、Super-P（0.1g）According to mass ratio 60:10:20:10 configuration resulting mixtures, are added solvent NMP（2.5g）, stir
Mix the electrode slurry that dark thick is prepared into after 2h.Electrode slurry is coated on metal copper foil, coating thickness is 20 μm；First exist
Forced air drying 3h at 120 DEG C, then 100 DEG C of vacuum drying 9h, are made lithium ion cell electrode piece.Obtained electrode slice mold
The round pole piece for being cut into a diameter of 14mm is used as the cathode of lithium-ion button battery, and metal lithium sheet is used as to electrode, and electrolyte is：
1mol/L LiPF6It is dissolved in EC and DMC（Molar ratio EC：DMC=1:1）, 2025 are assembled into the glove box full of argon gas
Type button cell.
XRD analysis is carried out to the Zn-bPTA materials synthesized by example 1, as can be seen from Figure 1 the XRD spectrums of powder diffraction
The characteristic peak of figure is consistent with the characteristic peak positions of theoretical modeling, illustrates the knot of the structure and simulation of synthesized Zn-bPTA materials
Structure is consistent.Fig. 2 is SEM morphology analysis and EDX energy spectrum analysis.Synthesized material granule is gill shape, and power spectrum elemental analysis is aobvious
Show that it is C, N, O, Zn to contain in example 1.Fig. 3 is the cyclic voltammetric of example 1（CV）Curve, it can be seen that have obviously in 0.1V or so
Reduction peak, 0.3V is corresponding with oxidation peak.Battery charging and discharging test result shows that Fig. 4 is head under the current density of 100mA/g
Secondary specific discharge capacity reaches 830mAhg-1, 100 times cycle after specific discharge capacity reach 380mAhg-1.The cycle that Fig. 5 is 100 times
Curve, after the 2nd time is recycled to the 100th cycle, capacity retention ratio 94.8%.
Embodiment 2：By Zn (NO3)2·6H2O (2.0 mmol, 594 mg)、H2bcbpy·2Cl (1.0 mmol,
516 mg)、HOOCC6H4COOH(2.0 mmol, 332 mg)、NH4PF6(2.0 mmol, 326 mg) are mixed, and are added to distillation
In the mixed solution of water (16 mL) and DMF (16 mL), 60min is stirred under air at room temperature atmosphere.Then mixing liquid is turned
It moves on in 50 ml Teflon autoclaves, is heated to 120 C constant temperature, 24 h.Cooled down after reaction with the rate of 10 DEG C/h
To room temperature, obtain white needle-like crystals, be filtered, washed, dry after obtain the complex Zn-bPTA, calculation of yield is about
82%.It will obtain the ground 300 mesh sieve of Zn-bPTA electrode materials.By metal complex Zn-bPTA（0.5g）、PVDF（0.1g）、
KS6（0.2g）、Super-P（0.2g）According to mass ratio 50:10:20:20 configuration resulting mixtures, are added solvent NMP（2.5g）, stir
Mix the electrode slurry that dark thick is prepared into after 2h.Electrode slurry is coated on metal copper foil, coating thickness is 30 μm；First exist
Forced air drying 3h at 120 DEG C, then 100 DEG C of vacuum drying 9h, are made lithium ion cell electrode piece.Obtained electrode slice mold
The round pole piece for being cut into a diameter of 14mm is used as the cathode of lithium-ion button battery, and metal lithium sheet is used as to electrode, and electrolyte is：
1mol/L LiPF6It is dissolved in EC and DMC（Molar ratio EC：DMC=1:1）, 2025 are assembled into the glove box full of argon gas
Type button cell.
XRD analysis is carried out to the Zn-bPTA materials synthesized by example 2, as can be seen from Figure 6 the XRD spectrums of powder diffraction
The characteristic peak of figure is consistent with the characteristic peak positions of theoretical modeling, the structure and example of the Zn-bPTA materials synthesized by illustrated example 2
Structure synthesized by 1 is consistent.Fig. 7 is SEM morphology analysis and EDX energy spectrum analysis.Synthesized material granule is gill shape, power spectrum
Elemental analysis, which is shown in Zn-bPTA synthesized by example 2, equally contains only the elements such as C, N, O, Zn.Fig. 8 is that example 2 synthesizes Zn-
The CV curves of bPTA materials, it can also be seen that having apparent redox peaks in 0.3V and 0.1V or so.Battery charging and discharging is surveyed
Test result shows that Fig. 9 is under the current density of 100mA/g, and first discharge specific capacity reaches 8270mAhg-1, 100 times cycle after put
Electric specific capacity reaches 410mAhg-1.Figure 10 is under the current density of 200mA/g, and the cyclic curve after 1000 cycles follows for the 2nd time
Ring is recycled to the 1000th time, and capacity retention ratio 93.1% illustrates that Zn-bPTA materials have as lithium ion battery negative material
Extraordinary cyclical stability.
The present invention selects the '-connection pyrrole of chlorination -1,1 '-two (3- carboxyls-benzylidene) -4,4 containing aromatic rings and carboxyl
Pyridine, terephthalic acid (TPA) and Zn2+Ion carries out reaction and prepares complex, and zinc-base complex is obtained by solvent thermal reaction（Abbreviation Zn-
bPTA）, which is used as lithium ion battery negative material, shows higher specific capacity and cyclical stability.It is right at present
In the research of complex electrode material, have that synthetic method is simple, high power capacity, high circulation stability, can be directly used in electrode material
The research of material is still very rare, therefore the research of this patent has a good application prospect.
Claims (10)
1. a kind of preparation method of zinc-base complex lithium ion battery negative material, including prepared by zinc-base complex, electrode slurry
It prepares, electrode slurry is dry and is assembled into button cell technique；It is characterized in that specific steps include as follows：
（1）Zn(NO3)2·6H2O（Zinc nitrate）、H2Bcbpy2Cl [chlorinations -1,1 '-two (3- carboxyls-benzylidene) -4,4 ' -
Bipyridyl], HOOCC6H4COOH（Terephthalic acid (TPA)）、NH4PF6（Ammonium hexafluorophosphate）According to molar ratio 2:1:2:2 ratio, adds
Enter to distilled water and DMF（N, N- dimethylformamide）Mixed solution（Volume ratio 1:1）In, stir 30min under air at room temperature atmosphere；
（2）By step（1）Mixture after middle stirring is transferred in the Teflon autoclave of 25mL, temperature 110~130
℃；Reaction time be 20~for 24 hours, be cooled to room temperature after reaction with the rate of temperature fall of 10 DEG C/h, obtain white needle-like crystals；
（3）By step（2）In obtain white needle-like crystals and be washed with distilled water, filter 2 times, be dried in vacuo at 80~100 DEG C
10~12h obtains zinc-base complex Zn-bPTA；
（4）By step（3）In obtain zinc-base complex Zn-bPTA, PVDF（Kynoar）、KS6（Electrically conductive graphite）、Super-
P（Super carbon black）According to mass ratio 60:10:20:10 or 50:10:20:20 configuration resulting mixtures, in mass ratio 1:2.5-4 plus
Enter solvent NMP（N-Methyl pyrrolidone）In, the electrode slurry of dark thick is prepared into after stirring 2h；
（5）By step（4）In obtained dark thick electrode slurry, be coated on metal copper foil, coating thickness is 20 μm~50 μ
M, coated electrode first with dry 6~12h under 120 DEG C of forced air drying 3h or more, then 100 DEG C of vacuum, obtain preparing lithium ion
The electrode of battery；
（6）By step（5）In obtained battery electrode be cut into the round pole piece of a diameter of 14mm, the metal lithium sheet of a diameter of 14mm
As to electrode, electrolyte is：1mol/L LiPF6It is dissolved in ethylene carbonate（EC）And dimethyl carbonate（DMC）Solvent in
（Molar ratio EC：DMC=1:1）, in the glove box full of argon gas, it is assembled into 2025 type button cells.
2. the preparation method of zinc-base complex lithium ion battery negative material according to claim 1, it is characterised in that：Institute
State Zn (NO3)2·6H2O、H2bcbpy·2Cl、HOOCC6H4COOH、NH4PF6, it is that analysis is pure.
3. the preparation method of zinc-base complex lithium ion battery negative material according to claim 1 or 2 it is characterized in that：
Zn (the NO3)2·6H21~4mmol is added according to the volume of reaction kettle in O；H2Bcbpy2Cl adds according to the volume of reaction kettle
Enter 0.5~2mmol；HOOCC6H41~4mmol is added according to the volume of reaction kettle in COOH；NH4PF6Added according to the volume of reaction kettle
Enter 1~4mmol；Teflon reaction kettle volume is 25~100mL.
4. the preparation method of zinc-base complex lithium ion battery negative material according to claim 1 or 2, feature exist
In：Zn (the NO3)2·6H2O、 H2bcbpy·2Cl、HOOCC6H4COOH、NH4PF6Ratio according to molar ratio 2:1:2:2 into
Row is mixed uniformly.
5. the preparation method of zinc-base complex lithium ion battery negative material according to claim 1, it is characterised in that：Institute
It is distilled water and DMF mixed solutions, volume ratio 1 to state solvent:1, volume be adapted reaction kettle in addition be 25~
100mL。
6. the preparation method of zinc-base complex lithium ion battery negative material according to claim 1, it is characterised in that：Institute
State step（1）In mixing time be 30~60min, stir speed (S.S.) be 500~800 r/min.
7. the preparation method of zinc-base complex lithium ion battery negative material according to claim 1, it is characterised in that：Institute
State step（2）In reaction temperature be 120 DEG C, the reaction time for 24 hours, room is cooled to the rate of temperature fall of 10 DEG C/h after reaction
Temperature.
8. the preparation method of zinc-base complex lithium ion battery negative material according to claim 1, it is characterised in that：Institute
State step（3）In it is washed after filter, be dried in vacuo 12h at 80 DEG C.
9. the preparation method of zinc-base complex lithium ion battery negative material according to claim 1, it is characterised in that：Institute
State step（4）Middle complex Zn-bPTA, PVDF, KS6, Super-P are according to mass ratio 60:10:20:10 or 50:10:20:20；
The amount that NMP is added is 2.5 times of mixture Zn-bPTA, PVDF, KS6, Super-P total weight.
10. the preparation method of zinc-base complex lithium ion battery negative material according to claim 1, it is characterised in that：
The step（5）Middle electrode slurry coating thickness is the thickness of any data in 20~50 μm；Forced air drying 3h at 120 DEG C,
100 DEG C of vacuum drying 9h again.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112803083A (en) * | 2021-02-08 | 2021-05-14 | 江苏师范大学 | Zinc ion battery containing zinc complex |
| CN113764688A (en) * | 2021-08-27 | 2021-12-07 | 北京工业大学 | Three-dimensional carbon structure supported GaN catalyst and preparation method thereof |
| CN114751462A (en) * | 2022-03-17 | 2022-07-15 | 吉林师范大学 | Preparation method of Cd-MOF derivative material based on iron ion exchange and application of Cd-MOF derivative material in lithium ion battery cathode |
| KR20230088835A (en) * | 2020-11-26 | 2023-06-20 | 지앙수 시케신카이 컴퍼니 리미티드 | UV blocking and blue light blocking optical materials and manufacturing methods thereof |
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| KR20230088835A (en) * | 2020-11-26 | 2023-06-20 | 지앙수 시케신카이 컴퍼니 리미티드 | UV blocking and blue light blocking optical materials and manufacturing methods thereof |
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| CN112803083A (en) * | 2021-02-08 | 2021-05-14 | 江苏师范大学 | Zinc ion battery containing zinc complex |
| CN113764688A (en) * | 2021-08-27 | 2021-12-07 | 北京工业大学 | Three-dimensional carbon structure supported GaN catalyst and preparation method thereof |
| CN113764688B (en) * | 2021-08-27 | 2024-02-06 | 北京工业大学 | Three-dimensional carbon structure supported GaN catalyst and preparation method thereof |
| CN114751462A (en) * | 2022-03-17 | 2022-07-15 | 吉林师范大学 | Preparation method of Cd-MOF derivative material based on iron ion exchange and application of Cd-MOF derivative material in lithium ion battery cathode |
| CN114751462B (en) * | 2022-03-17 | 2023-10-03 | 吉林师范大学 | Preparation method of Cd-MOF derivative material based on iron ion exchange and application of derivative material in aspect of lithium ion battery cathode |
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