CN107359350A - Preparation method with excellent electrochemical performance iron Zn complex and its derivative - Google Patents
Preparation method with excellent electrochemical performance iron Zn complex and its derivative Download PDFInfo
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- CN107359350A CN107359350A CN201710279919.2A CN201710279919A CN107359350A CN 107359350 A CN107359350 A CN 107359350A CN 201710279919 A CN201710279919 A CN 201710279919A CN 107359350 A CN107359350 A CN 107359350A
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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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
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Preparation method with excellent electrochemical performance iron Zn complex and its derivative, the polymer are prepared by the component of following quality point：1.0 ~ 2.0 parts of zinc acetate, 1.0 ~ 2.0 parts of frerrous chloride, 2.0 ~ 3.0 parts of lithium sulfate, 12.0 ~ 14.0 parts of Pyromellitic Acid and 10.0 ~ 15.0 parts of lithium hydroxide.Particularly advantage of the invention is as follows：First, preparation method is simple and convenient, without using strong acid and strong base, strong oxidizer and toxic reagent in preparation process.Second, the product sintered in nitrogen, in the case where current density is 50mA/g, specific capacity is up to 1364mAh/g, and specific capacity can still remain 230mAh/g after circulating 100 cycles.By graphene and metal organic coordination polymer carry out it is compound after test its chemical property, it is found that graphene causes the metal organic coordination polymer of original no chemical property to show higher charging and discharging capacity and good cycle performance.Under 50mA/g current density, specific capacity is 1090mAh/g first, and after the circulation in 100 cycles, specific capacity can still be stablized near 305mAh/g.
Description
Technical field
The present invention relates to it is a kind of with excellent electrochemical performance zinc ion doping ferrous metal organic coordination polymer and
The preparation method of its compound derivative, belong to electrochemical material preparation field.
Background technology
In today's society, substantial amounts of pernicious gas is produced with the burning of fossil fuel so that environmental pollution phenomenon is got over
Carry out more serious, the exhaustion of this non-renewable energy resources so that people are continuously increased to the demand of the energy.Therefore exploitation one kind can be again
Raw and sustainable development the energy, is all circles of world focus of attention to solve the crisis of the existing energy and environment.When
Before, people have developed and utilized a variety of effective and reliable energy, such as lithium ion battery, solar cell are super
Capacitor etc..Wherein lithium ion battery is because it has high an operating voltage and energy density, memory-less effect, self-discharge rate compared with
Low, cycle performance is good, will not to environment and human body according into the advantages that harm as the focus of people's research.
Traditional lithium ion battery negative material far can not meet the needs of people's life, develop new negative pole
Material is extremely urgent.
The content of the invention
Goal of the invention
The present invention provide a kind of zinc ion doping ferrous metal organic coordination polymer for having an excellent electrochemical performance and its
The compound derivant material of series, it is the problems of conventional the purpose is to solve.
Technical scheme：
A kind of zinc ion doping iron content coordination polymer with excellent electrochemical performance, it is characterised in that：The polymer
It is prepared by the component of following quality point：1.0~2.0 parts of zinc acetate, 1.0~2.0 parts of frerrous chloride, 2.0~3.0 parts
Lithium sulfate, 12.0~14.0 parts of Pyromellitic Acid and 10.0~15.0 parts of lithium hydroxide.
The polymer is the polymer of the excellent electrochemical performance shown in lithium ion battery.
The method for preparing the above-mentioned doping iron content coordination polymer of the zinc ion with excellent electrochemical performance, its feature exist
In：This method is as follows：The preparation of the polymer and its compound derivative uses simple hydrothermal synthesis method and subsequent lehr attendant
Skill, specially by 1.0~2.0 parts of zinc acetate, 1.0~2.0 parts of frerrous chloride, 2.0~3.0 parts of lithium sulfate, 12.0~
14.0 parts of Pyromellitic Acid and 10.0~15.0 parts of lithium hydroxide are dissolved in 8~15ml water, magnetic agitation half an hour
It is placed in afterwards in the reactor of the polytetrafluoroethyllining lining of 15-50ml capacity, reactor is sealed and is maintained at temperature range is
24-72 hour hydrothermal synthesis reactions are carried out at 120-180 DEG C, 0 DEG C -35 DEG C is then naturally cooled to, precursor is filtered out, with nothing
Water-ethanol and distilled water wash the solid particle for several times, being then collected into and are dried overnight at room temperature or 60 DEG C respectively.
At 400-600 DEG C, dried precursor is heat-treated, 3-6 hours are kept in air atmosphere
Obtain carbon composite oxides；Or constant temperature 3-6 hours obtain carbon coating oxide and answered in nitrogen atmosphere of the concentration more than 99.9%
Condensation material.That is, the presoma prepared is dried overnight in room temperature or 60 DEG C of temperature ranges, and annealing reaction is 400- in temperature
600 DEG C, kept for about 3-6 hours in air or nitrogen atmosphere.
The graphene that metal coordinating polymer precursor adds not more than 10% carries out ultrasound and milled processed, obtains graphite
Alkene coats metal coordinating polymer composite.
The graphene progress ultrasound and milled processed for being not more than precursor quality 10% are added, obtains graphene bag
Metal coordinating polymer is covered, and it is heat-treated at 400-600 DEG C, is kept for 3-6 hours obtain stone in air atmosphere
The compound of black alkene and carbon coating oxide, i.e. graphene/carbon/zinc oxide/ferroso-ferric oxide.
First spirit solvent is filtered, is then made again using accumulative 10~50 milliliters of washings of absolute ethyl alcohol after precursor is filtered out
With accumulative 30~60 milliliters distillation water washing for several times.
Absolute ethyl alcohol concentration is 96%~100%, and room temperature is 0 DEG C -25 DEG C.
Carbon composite oxides are carbon/zinc oxide/ferroso-ferric oxide, and carbon coating oxide is carbon/zinc ferrite.
Zinc ion doping iron content coordination polymer and its derivant material described above with excellent electrochemical performance are used
On the way, it is characterised in that：It is applied in lithium ion battery.
High specific capacity and good cycle performance are shown in lithium ion battery.
Advantage and effect
The invention provides a kind of lithium ion battery negative material and preparation method thereof, it meets negative electrode of lithium ion battery
The requirement of the high specific capacity of material and good cycle performance, the material are with simple hydrothermal synthesis method and subsequent annealing
Technique is prepared, in addition, preparation process condition is gentleer, without using strong acid and strong base, strong oxidizer and toxic reagent, synthesis
Method is simple and cheap, can on a large scale be synthesized, had a good application prospect.
Compared with inorganic matter, metal organic coordination polymer has obvious superiority condition, and it has, and specific surface area is big, hole
The advantages that gap rate is high, turn into the focus of people's research and concern.Metal organic coordination polymer influence factor it is maximum for metal
With the property of organic ligand, while also other influence factors, such as pH value, metal proportioning, the factor such as temperature.Metal is had
Machine coordination polymer carries out calcining as presoma and can obtain metal oxide and the metal oxide of carbon coating, as lithium
The negative material of ion battery can be used for supplementing deficiency of traditional carbon material as negative material, to meet in people's life
To the more preferable demand of lithium ion battery, hair outputs the new lithium ion battery with more height ratio capacity.
Particularly advantage of the invention is as follows：
First, preparation method is simple and convenient, without using strong acid and strong base, strong oxidizer and toxic reagent in preparation process, closes
It is simple and cheap into method, it can on a large scale be synthesized, be had a good application prospect.
Second, its electrochemistry is tested after metal organic coordination polymer is sintered in air and nitrogen respectively
Can, the product sintered in atmosphere is found, the specific capacity in the case where current density is 50mA/g with 3082mAh/g, but it is circulated
Stability is not good enough.The product sintered in nitrogen, in the case where current density is 50mA/g, specific capacity is up to 1364mAh/g, circulation
Specific capacity can still remain 230mAh/g after 100 cycles.Graphene and metal organic coordination polymer are subjected to compound rear survey
Its chemical property is tried, it is found that it is higher graphene make it that the metal organic coordination polymer of original no chemical property is shown
Charging and discharging capacity and good cycle performance.Under 50mA/g current density, specific capacity is 1090mAh/g first, 100
After the circulation in individual cycle, specific capacity can still be stablized near 305mAh/g.
Brief description of the drawings
Fig. 1 is the preparation flow figure of the present invention.
Embodiment
Embodiment 1：
By 1.0~2.0 parts of zinc acetate, 1.0~2.0 parts of frerrous chloride, 2.0~3.0 parts of lithium sulfate, 12.0~
14.0 parts of Pyromellitic Acid and 10.0~15.0 parts of lithium hydroxide are dissolved in 8~15ml water, and magnetic agitation causes solution
It is well mixed, in the reactor for the polytetrafluoroethyllining lining for being subsequently placed in 15-50ml capacity, reactor is sealed and in humidity province
Between be 120-180 DEG C at keep 24-72 hours, then naturally cool to room temperature, precursor filtered out, with ethanol and distillation moisture
Do not wash for several times, be then dried overnight at room temperature (0~35 DEG C) or 60 DEG C；Described precursor is entered at 400-600 DEG C
Row heat treatment, keeps about 3-6 hours to obtain product (carbon/zinc oxide/ferroso-ferric oxide), labeled as Fe1 in air atmosphere.
By Fe1, conductive acetylene is black, and Kynoar (PVDF) is with 7：2：1 ratio is well mixed.Add appropriate solvent
1-METHYLPYRROLIDONE (NMP), is fully ground to form uniform starchiness, and slurry is uniformly coated in into copper foil surface, then will be applied
Good electrode slice is placed in vacuum drying chamber at 100-120 DEG C to be more than 10 hours and dried.The pole piece of taking-up is put on tablet press machine
Apply certain pressure, to improve the adhesion between negative material and copper foil, prevent negative electrode material layer in Electrochemical Test Procedure
Fall off.The pole piece pressed is dried, then cut, and weigh the quality of each electrode slice.Being assembled in for battery is filled
Completed in the glove box of full high-purity argon gas atmosphere protection, load weighted pole piece is set to working electrode, lithium piece is used as to electrode.Will
Negative electrode casing, spring leaf, iron plate, lithium piece, barrier film is put well successively in order, then is placed on electrode slice, is covered after instilling two drop electrolyte
Anode cover, button simulated battery has been assembled into it.The button cell assembled is taken out by the rule of glove box, immediately on sealing machine
Carry out sealing treatment.Electrochemical property test will be carried out after above-mentioned battery standing 4h.Using blue electrical testing system testing sample
Chemical property, test voltage scope are 0.01~2V, current density 50mA/g.Test result has in circulating first
3082mAh/g specific capacity, far above other lithium ion battery negative materials.
Embodiment 2：
By 1.0~2.0 parts of zinc acetate, 1.0~2.0 parts of frerrous chloride, 2.0~3.0 parts of lithium sulfate, 12.0~
14.0 parts of Pyromellitic Acid and 10.0~15.0 parts of lithium hydroxide are dissolved in 8~15ml water, magnetic agitation half an hour
It is placed in afterwards in the stainless steel cauldron of the polytetrafluoroethyllining lining of 15-50ml capacity, reactor is sealed and is maintained at humidity province
Between be that 24-72 hours are carried out at 120-180 DEG C, then naturally cool to room temperature, precursor filtered out, distinguished with ethanol and distilled water
Washing for several times, is then dried overnight at room temperature (0~35 DEG C) or 60 DEG C；Described precursor is carried out at 400-600 DEG C
Heat treatment, keeps about 3-6 hours to obtain product (carbon/zinc ferrite), labeled as Fe2 in nitrogen atmosphere.
By Fe2, conductive acetylene is black, and Kynoar (PVDF) is with 7：2：1 ratio is well mixed.Add appropriate solvent
1-METHYLPYRROLIDONE (NMP), is fully ground to form uniform starchiness, and slurry is uniformly coated in into copper foil surface, then will be applied
Good electrode slice is placed in vacuum drying chamber at 100-120 DEG C dries more than 10h.The pole piece of taking-up is put on tablet press machine and applied
Add certain pressure, to improve the adhesion between negative material and copper foil, prevent that negative electrode material layer is sent out in Electrochemical Test Procedure
Life comes off.Pole piece is dried, the pole piece pressed is cut, and weighs the quality of each electrode slice.Being assembled in for battery is full of
Completed in the glove box of high-purity argon gas atmosphere protection, using load weighted pole piece as working electrode, lithium piece is to electrode.By negative pole
Shell, spring leaf, iron plate, lithium piece, barrier film is put well successively in order, then is placed on electrode slice, and positive pole is covered after instilling two drop electrolyte
Shell, button simulated battery has been assembled into it.The button cell assembled is taken out by the rule of glove box, is carried out immediately on sealing machine
Sealing treatment.Electrochemical property test will be carried out after above-mentioned battery standing 4h.Using the electrification of blue electrical testing system testing sample
Performance is learned, test voltage scope is 0.01~2V, current density 50mA/g.Specific capacity during test result circulates first is reachable
1364mAh/g, specific capacity can still remain 230mAh/g after circulating 100 cycles.
Embodiment 3：
By 1.0~2.0 parts of zinc acetate, 1.0~2.0 parts of frerrous chloride, 2.0~3.0 parts of lithium sulfate, 12.0~
14.0 parts of Pyromellitic Acid and 10.0~15.0 parts of lithium hydroxide are dissolved in 8~15ml water, magnetic agitation half an hour
It is placed in afterwards in the reactor of the polytetrafluoroethyllining lining of 15-50ml capacity, reactor is sealed and is maintained at temperature range is
24-72 hours are carried out at 120-180 DEG C, room temperature is then naturally cooled to, precursor is filtered out, with ethanol and distillation water washing number
It is secondary, then it is dried overnight at room temperature (0~35 DEG C) or 60 DEG C；The graphene that addition is not more than 10% is ultrasonically treated to obtain
The metal organic coordination polymer of graphene coated is labeled as Fe3.
By Fe3, conductive acetylene is black, and Kynoar (PVDF) is with 7：2：1 ratio is well mixed.Add appropriate solvent
1-METHYLPYRROLIDONE (NMP), it is fully ground to be formed and starchiness, slurry is uniformly coated in copper foil surface, then will applies
Good electrode slice is placed in vacuum drying chamber at 100-120 DEG C dried more than 10 hours.The pole piece of taking-up is put into tablet press machine
It is upper to apply certain pressure, to improve the adhesion between negative material and copper foil, prevent negative material in Electrochemical Test Procedure
Layer is fallen off.Pole piece is dried, the pole piece pressed is cut, and weighs the quality of each electrode slice.Battery is assembled in
Completed in glove box full of high-purity argon gas atmosphere protection, using load weighted pole piece as working electrode, lithium piece is to electrode.Will
Negative electrode casing, spring leaf, iron plate, lithium piece, barrier film is put well successively in order, then is placed on electrode slice, is covered after instilling two drop electrolyte
Anode cover, button simulated battery has been assembled into it.The button cell assembled is taken out by the rule of glove box, immediately on sealing machine
Carry out sealing treatment.Electrochemical property test will be carried out after above-mentioned battery standing 4h.Using blue electrical testing system testing sample
Chemical property, test voltage scope are 0.01~2V, current density 50mA/g.Specific capacity is 1090mAh/g first, 100
After the circulation in individual cycle, specific capacity can still be stablized near 305mAh/g, add coordination polymer stable circulation after graphene
Property greatly improves.
Embodiment 4：
By 1.0~2.0 parts of zinc acetate, 1.0~2.0 parts of frerrous chloride, 2.0~3.0 parts of lithium sulfate, 12.0~
14.0 parts of Pyromellitic Acid and 10.0~15.0 parts of lithium hydroxide are dissolved in 8~15ml water, magnetic agitation half an hour
It is placed in afterwards in the reactor of the polytetrafluoroethyllining lining of 15-50ml capacity, reactor is sealed and is maintained at temperature range is
24-72 hours are carried out at 120-180 DEG C, room temperature is then naturally cooled to, precursor is filtered out, washed respectively with ethanol and distilled water
Wash for several times, be then dried overnight at room temperature (0~35 DEG C) or 60 DEG C；The graphene that addition is not more than 10% is ultrasonically treated
Graphene coated metal organic coordination polymer is obtained, is heat-treated described precursor at 400-600 DEG C, in air
About 3-6 hours are kept to obtain product (graphene/carbon/zinc oxide/ferroso-ferric oxide) in atmosphere, labeled as Fe4.
By Fe4, conductive acetylene is black, and Kynoar (PVDF) is with 7：2：1 ratio is well mixed.Add appropriate solvent
1-METHYLPYRROLIDONE (NMP), is fully ground to form uniform starchiness, and slurry is uniformly coated in into copper foil surface, then will be applied
Good electrode slice is placed in vacuum drying chamber at 100-120 DEG C dried more than 10 hours.The pole piece of taking-up is put into tablet press machine
It is upper to apply certain pressure, to improve the adhesion between negative material and copper foil, prevent negative material in Electrochemical Test Procedure
Layer is fallen off.Electrode slice is dried, the electrode slice pressed is cut, and weighs the quality of each electrode slice.The group of battery
Completed in the glove box full of atmosphere protection, using load weighted electrode slice as working electrode, lithium piece is to electrode.Will be negative
Pole shell, spring leaf, iron plate, lithium piece, barrier film is put well successively in order, then is placed on electrode slice, is covered just after instilling two drop electrolyte
Pole shell, button simulated battery has been assembled into it.The button cell assembled is taken out by the rule of glove box, it is enterprising in sealing machine immediately
Row sealing treatment.Electrochemical property test will be carried out after above-mentioned battery standing 4h.Using the electricity of blue electrical testing system testing sample
Chemical property, test voltage scope are 0.01~2V, current density 50mA/g.Charging and discharging capacity first is respectively
669mAh/g, 1405mAh/g, the specific capacity circulated after 100 cycles is still 258mAh/g.
Embodiment 5：
By 1.0 parts of zinc acetate, 1.0 parts of frerrous chloride, 2.0 parts of lithium sulfate, 12.0 parts of Pyromellitic Acid and
10.0 parts of lithium hydroxide is dissolved in 8ml water, and magnetic agitation causes solution to be well mixed, and is subsequently placed in poly- the four of 15ml capacity
In the reactor of PVF liner, reactor is sealed and is kept for 24 hours at being 120 DEG C in temperature range, then natural cooling
To room temperature, precursor is filtered out, washed respectively for several times with ethanol and distilled water, is then done at room temperature (0~35 DEG C) or 60 DEG C
It is dry overnight；Described precursor is heat-treated at 400 DEG C, keep obtaining for about 3 hours in air atmosphere product (carbon/
Zinc oxide/ferroso-ferric oxide), labeled as Fe5.
By Fe5, conductive acetylene is black, and Kynoar (PVDF) is with 7：2：1 ratio is well mixed.Add appropriate solvent
1-METHYLPYRROLIDONE (NMP), is fully ground to form uniform starchiness, and slurry is uniformly coated in into copper foil surface, then will be applied
Good electrode slice is placed in vacuum drying chamber at 100-120 DEG C to be more than 10 hours and dried.The pole piece of taking-up is put on tablet press machine
Apply certain pressure, to improve the adhesion between negative material and copper foil, prevent negative electrode material layer in Electrochemical Test Procedure
Fall off.The pole piece pressed is dried, then cut, and weigh the quality of each electrode slice.Being assembled in for battery is filled
Completed in the glove box of full high-purity argon gas atmosphere protection, load weighted pole piece is set to working electrode, lithium piece is used as to electrode.Will
Negative electrode casing, spring leaf, iron plate, lithium piece, barrier film is put well successively in order, then is placed on electrode slice, is covered after instilling two drop electrolyte
Anode cover, button simulated battery has been assembled into it.The button cell assembled is taken out by the rule of glove box, immediately on sealing machine
Carry out sealing treatment.Electrochemical property test will be carried out after above-mentioned battery standing 4h.Using blue electrical testing system testing sample
Chemical property, test voltage scope are 0.01~2V, current density 50mA/g.Test result has in circulating first
3091mAh/g specific capacity, far above other lithium ion battery negative materials.
Embodiment 6：
By 2.0 parts of zinc acetate, 2.0 parts of frerrous chloride, 3.0 parts of lithium sulfate, 14.0 parts of Pyromellitic Acid and
15.0 parts of lithium hydroxide is dissolved in 15ml water, and magnetic agitation causes solution to be well mixed, and is subsequently placed in the poly- of 50ml capacity
In the reactor of tetrafluoroethene liner, reactor is sealed and kept for 72 hours at being 1180 DEG C in temperature range, it is then natural
Room temperature is cooled to, precursor is filtered out, is washed respectively for several times with ethanol and distilled water, then in room temperature (0~35 DEG C) or 60 DEG C
Under be dried overnight；Described precursor is heat-treated at 600 DEG C, keeps obtaining product in about 6 hours in air atmosphere
(carbon/zinc oxide/ferroso-ferric oxide), labeled as Fe6.
By Fe6, conductive acetylene is black, and Kynoar (PVDF) is with 7：2：1 ratio is well mixed.Add appropriate solvent
1-METHYLPYRROLIDONE (NMP), is fully ground to form uniform starchiness, and slurry is uniformly coated in into copper foil surface, then will be applied
Good electrode slice is placed in vacuum drying chamber at 100-120 DEG C to be more than 10 hours and dried.The pole piece of taking-up is put on tablet press machine
Apply certain pressure, to improve the adhesion between negative material and copper foil, prevent negative electrode material layer in Electrochemical Test Procedure
Fall off.The pole piece pressed is dried, then cut, and weigh the quality of each electrode slice.Being assembled in for battery is filled
Completed in the glove box of full high-purity argon gas atmosphere protection, load weighted pole piece is set to working electrode, lithium piece is used as to electrode.Will
Negative electrode casing, spring leaf, iron plate, lithium piece, barrier film is put well successively in order, then is placed on electrode slice, is covered after instilling two drop electrolyte
Anode cover, button simulated battery has been assembled into it.The button cell assembled is taken out by the rule of glove box, immediately on sealing machine
Carry out sealing treatment.Electrochemical property test will be carried out after above-mentioned battery standing 4h.Using blue electrical testing system testing sample
Chemical property, test voltage scope are 0.01~2V, current density 50mA/g.Test result has in circulating first
3079mAh/g specific capacity, far above other lithium ion battery negative materials.
Embodiment 7：
By 1.0 parts of zinc acetate, 1.0 parts of frerrous chloride, 2.0 parts of lithium sulfate, 12.0 parts of Pyromellitic Acid and
10.0 parts of lithium hydroxide is dissolved in 8ml water, and the polytetrafluoroethyllining lining of 15ml capacity is placed in after magnetic agitation half an hour
Stainless steel cauldron in, reactor is sealed and is maintained at temperature range to carry out 24 hours at 120 DEG C, then natural cooling
To room temperature, precursor is filtered out, washed respectively for several times with ethanol and distilled water, is then dried at room temperature (0~35 DEG C) or 60 DEG C
Overnight；Described precursor is heat-treated at 400 DEG C, keeps obtaining product (carbon/iron in about 3 hours in nitrogen atmosphere
Sour zinc), labeled as Fe7.
By Fe7, conductive acetylene is black, and Kynoar (PVDF) is with 7：2：1 ratio is well mixed.Add appropriate solvent
1-METHYLPYRROLIDONE (NMP), is fully ground to form uniform starchiness, and slurry is uniformly coated in into copper foil surface, then will be applied
Good electrode slice is placed in vacuum drying chamber at 100-120 DEG C dries more than 10h.The pole piece of taking-up is put on tablet press machine and applied
Add certain pressure, to improve the adhesion between negative material and copper foil, prevent that negative electrode material layer is sent out in Electrochemical Test Procedure
Life comes off.Pole piece is dried, the pole piece pressed is cut, and weighs the quality of each electrode slice.Being assembled in for battery is full of
Completed in the glove box of high-purity argon gas atmosphere protection, using load weighted pole piece as working electrode, lithium piece is to electrode.By negative pole
Shell, spring leaf, iron plate, lithium piece, barrier film is put well successively in order, then is placed on electrode slice, and positive pole is covered after instilling two drop electrolyte
Shell, button simulated battery has been assembled into it.The button cell assembled is taken out by the rule of glove box, is carried out immediately on sealing machine
Sealing treatment.Electrochemical property test will be carried out after above-mentioned battery standing 4h.Using the electrification of blue electrical testing system testing sample
Performance is learned, test voltage scope is 0.01~2V, current density 50mA/g.Specific capacity during test result circulates first is reachable
1367mAh/g, specific capacity can still remain 232mAh/g after circulating 100 cycles.
Embodiment 8：
By 2.0 parts of zinc acetate, 2.0 parts of frerrous chloride, 3.0 parts of lithium sulfate, 14.0 parts of Pyromellitic Acid and
15.0 parts of lithium hydroxide is dissolved in 15ml water, and the polytetrafluoroethyllining lining of 50ml capacity is placed in after magnetic agitation half an hour
Stainless steel cauldron in, reactor is sealed and is maintained at temperature range to carry out 72 hours at 180 DEG C, then natural cooling
To room temperature, precursor is filtered out, washed respectively for several times with ethanol and distilled water, is then dried overnight at 60 DEG C of room temperature；At 600 DEG C
It is lower to be heat-treated described precursor, keep obtaining within about 6 hours product (carbon/zinc ferrite) in nitrogen atmosphere, be labeled as
Fe8。
By Fe8, conductive acetylene is black, and Kynoar (PVDF) is with 7：2：1 ratio is well mixed.Add appropriate solvent
1-METHYLPYRROLIDONE (NMP), is fully ground to form uniform starchiness, and slurry is uniformly coated in into copper foil surface, then will be applied
Good electrode slice is placed in vacuum drying chamber at 100-120 DEG C dries more than 10h.The pole piece of taking-up is put on tablet press machine and applied
Add certain pressure, to improve the adhesion between negative material and copper foil, prevent that negative electrode material layer is sent out in Electrochemical Test Procedure
Life comes off.Pole piece is dried, the pole piece pressed is cut, and weighs the quality of each electrode slice.Being assembled in for battery is full of
Completed in the glove box of high-purity argon gas atmosphere protection, using load weighted pole piece as working electrode, lithium piece is to electrode.By negative pole
Shell, spring leaf, iron plate, lithium piece, barrier film is put well successively in order, then is placed on electrode slice, and positive pole is covered after instilling two drop electrolyte
Shell, button simulated battery has been assembled into it.The button cell assembled is taken out by the rule of glove box, is carried out immediately on sealing machine
Sealing treatment.Electrochemical property test will be carried out after above-mentioned battery standing 4h.Using the electrification of blue electrical testing system testing sample
Performance is learned, test voltage scope is 0.01~2V, current density 50mA/g.Specific capacity during test result circulates first is reachable
1364mAh/g, specific capacity can still remain 230mAh/g after circulating 100 cycles.
Embodiment 9：
By 1.0 parts of zinc acetate, 1.0 parts of frerrous chloride, 2.0 parts of lithium sulfate, 12.0 parts of Pyromellitic Acid and
10.0 parts of lithium hydroxide is dissolved in 8ml water, and the polytetrafluoroethyllining lining of 15ml capacity is placed in after magnetic agitation half an hour
Reactor in, reactor is sealed and is maintained at temperature range to carry out 24 hours at 120 DEG C, then naturally cools to room
Temperature, precursor is filtered out, with ethanol and distill water washing for several times, be then dried overnight at room temperature (0~35 DEG C) or 60 DEG C；Add
The metal organic coordination polymer that 8% graphene is ultrasonically treated to obtain graphene coated is labeled as Fe9.
By Fe9, conductive acetylene is black, and Kynoar (PVDF) is with 7：2：1 ratio is well mixed.Add appropriate solvent
1-METHYLPYRROLIDONE (NMP), it is fully ground to be formed and starchiness, slurry is uniformly coated in copper foil surface, then will applies
Good electrode slice is placed in vacuum drying chamber at 100-120 DEG C dried more than 10 hours.The pole piece of taking-up is put into tablet press machine
It is upper to apply certain pressure, to improve the adhesion between negative material and copper foil, prevent negative material in Electrochemical Test Procedure
Layer is fallen off.Pole piece is dried, the pole piece pressed is cut, and weighs the quality of each electrode slice.Battery is assembled in
Completed in glove box full of high-purity argon gas atmosphere protection, using load weighted pole piece as working electrode, lithium piece is to electrode.Will
Negative electrode casing, spring leaf, iron plate, lithium piece, barrier film is put well successively in order, then is placed on electrode slice, is covered after instilling two drop electrolyte
Anode cover, button simulated battery has been assembled into it.The button cell assembled is taken out by the rule of glove box, immediately on sealing machine
Carry out sealing treatment.Electrochemical property test will be carried out after above-mentioned battery standing 4h.Using blue electrical testing system testing sample
Chemical property, test voltage scope are 0.01~2V, current density 50mA/g.Specific capacity is 1091mAh/g first, 100
After the circulation in individual cycle, specific capacity can still be stablized near 303mAh/g, add coordination polymer stable circulation after graphene
Property greatly improves.
Embodiment 10：
By 2.0 parts of zinc acetate, 2.0 parts of frerrous chloride, 3.0 parts of lithium sulfate, 14.0 parts of Pyromellitic Acid and
15.0 parts of lithium hydroxide is dissolved in 15ml water, and the polytetrafluoroethyllining lining of 50ml capacity is placed in after magnetic agitation half an hour
Reactor in, reactor is sealed and is maintained at temperature range to carry out 72 hours at 180 DEG C, then naturally cools to room
Temperature, precursor is filtered out, with ethanol and distill water washing for several times, be then dried overnight at room temperature (0~35 DEG C) or 60 DEG C；Add
The metal organic coordination polymer that 10% graphene is ultrasonically treated to obtain graphene coated is labeled as Fe10.
By Fe3, conductive acetylene is black, and Kynoar (PVDF) is with 7：2：1 ratio is well mixed.Add appropriate solvent
1-METHYLPYRROLIDONE (NMP), it is fully ground to be formed and starchiness, slurry is uniformly coated in copper foil surface, then will applies
Good electrode slice is placed in vacuum drying chamber at 100-120 DEG C dried more than 10 hours.The pole piece of taking-up is put into tablet press machine
It is upper to apply certain pressure, to improve the adhesion between negative material and copper foil, prevent negative material in Electrochemical Test Procedure
Layer is fallen off.Pole piece is dried, the pole piece pressed is cut, and weighs the quality of each electrode slice.Battery is assembled in
Completed in glove box full of high-purity argon gas atmosphere protection, using load weighted pole piece as working electrode, lithium piece is to electrode.Will
Negative electrode casing, spring leaf, iron plate, lithium piece, barrier film is put well successively in order, then is placed on electrode slice, is covered after instilling two drop electrolyte
Anode cover, button simulated battery has been assembled into it.The button cell assembled is taken out by the rule of glove box, immediately on sealing machine
Carry out sealing treatment.Electrochemical property test will be carried out after above-mentioned battery standing 4h.Using blue electrical testing system testing sample
Chemical property, test voltage scope are 0.01~2V, current density 50mA/g.Specific capacity is 1090mAh/g first, 100
After the circulation in individual cycle, specific capacity can still be stablized near 305mAh/g, add coordination polymer stable circulation after graphene
Property greatly improves.
Embodiment 11：
By 1.0 parts of zinc acetate, 1.0 parts of frerrous chloride, 2.0 parts of lithium sulfate, 12.0 parts of Pyromellitic Acid and
10.0 parts of lithium hydroxide is dissolved in 8ml water, and the polytetrafluoroethyllining lining of 15ml capacity is placed in after magnetic agitation half an hour
Reactor in, reactor is sealed and is maintained at temperature range to carry out 24 hours at 120 DEG C, then naturally cools to room
Temperature, precursor is filtered out, washed respectively for several times with ethanol and distilled water, it is then dried at room temperature (0~35 DEG C) or 60 DEG C
Night；The graphene of addition 6.5% is ultrasonically treated to obtain graphene coated metal organic coordination polymer, will at 400 DEG C
Described precursor is heat-treated, and keeps obtaining for about 3 hours the product (oxygen of graphene/carbon/zinc oxide/tetra- in air atmosphere
Change three-iron), labeled as Fe11.
By Fe11, conductive acetylene is black, and Kynoar (PVDF) is with 7：2：1 ratio is well mixed.Add in right amount molten
Agent 1-METHYLPYRROLIDONE (NMP), is fully ground to form uniform starchiness, and slurry is uniformly coated in into copper foil surface, then will
The electrode slice coated is placed in vacuum drying chamber at 100-120 DEG C dried more than 10 hours.The pole piece of taking-up is put into tabletting
Apply certain pressure on machine, to improve the adhesion between negative material and copper foil, prevent negative pole material in Electrochemical Test Procedure
The bed of material is fallen off.Electrode slice is dried, the electrode slice pressed is cut, and weighs the quality of each electrode slice.Battery
It is assembled in the glove box full of atmosphere protection and completes, using load weighted electrode slice as working electrode, lithium piece is to electrode.Will
Negative electrode casing, spring leaf, iron plate, lithium piece, barrier film is put well successively in order, then is placed on electrode slice, is covered after instilling two drop electrolyte
Anode cover, button simulated battery has been assembled into it.The button cell assembled is taken out by the rule of glove box, immediately on sealing machine
Carry out sealing treatment.Electrochemical property test will be carried out after above-mentioned battery standing 4h.Using blue electrical testing system testing sample
Chemical property, test voltage scope are 0.01~2V, current density 50mA/g.Charging and discharging capacity first is respectively
668mAh/g, 1406mAh/g, the specific capacity circulated after 100 cycles is still 258mAh/g.
Embodiment 12：
By 2.0 parts of zinc acetate, 2.0 parts of frerrous chloride, 3.0 parts of lithium sulfate, 14.0 parts of Pyromellitic Acid and
15.0 parts of lithium hydroxide is dissolved in 15ml water, and the polytetrafluoroethyllining lining of 50ml capacity is placed in after magnetic agitation half an hour
Reactor in, reactor is sealed and is maintained at temperature range to carry out 72 hours at 180 DEG C, then naturally cools to room
Temperature, precursor is filtered out, washed respectively for several times with ethanol and distilled water, it is then dried at room temperature (0~35 DEG C) or 60 DEG C
Night；The graphene of addition 10% is ultrasonically treated to obtain graphene coated metal organic coordination polymer, by institute at 600 DEG C
The precursor stated is heat-treated, and keeps obtaining for about 6 hours the product (oxidation of graphene/carbon/zinc oxide/tetra- in air atmosphere
Three-iron), labeled as Fe12.
By Fe12, conductive acetylene is black, and Kynoar (PVDF) is with 7：2：1 ratio is well mixed.Add in right amount molten
Agent 1-METHYLPYRROLIDONE (NMP), is fully ground to form uniform starchiness, and slurry is uniformly coated in into copper foil surface, then will
The electrode slice coated is placed in vacuum drying chamber at 100-120 DEG C dried more than 10 hours.The pole piece of taking-up is put into tabletting
Apply certain pressure on machine, to improve the adhesion between negative material and copper foil, prevent negative pole material in Electrochemical Test Procedure
The bed of material is fallen off.Electrode slice is dried, the electrode slice pressed is cut, and weighs the quality of each electrode slice.Battery
It is assembled in the glove box full of atmosphere protection and completes, using load weighted electrode slice as working electrode, lithium piece is to electrode.Will
Negative electrode casing, spring leaf, iron plate, lithium piece, barrier film is put well successively in order, then is placed on electrode slice, is covered after instilling two drop electrolyte
Anode cover, button simulated battery has been assembled into it.The button cell assembled is taken out by the rule of glove box, immediately on sealing machine
Carry out sealing treatment.Electrochemical property test will be carried out after above-mentioned battery standing 4h.Using blue electrical testing system testing sample
Chemical property, test voltage scope are 0.01~2V, current density 50mA/g.Charging and discharging capacity first is respectively
669mAh/g, 1405mAh/g, the specific capacity circulated after 100 cycles is still 258mAh/g.
In summary, new zinc ion doping has excellent chemical property containing iron complex and its derivative, its
The product sintered in air has the specific capacity higher than other negative materials, and the product specific capacity sintered in nitrogen is higher, follows
Ring performance is good；With graphene it is compound after, its chemical property significantly improves, while graphene coated coordination polymer and graphene
The oxide coated circulating battery stability all than independent coordination polymer and oxide alone greatly improves.
Claims (11)
- A kind of 1. zinc ion doping iron content coordination polymer with excellent electrochemical performance, it is characterised in that：The polymer by The component of following quality point is prepared：1.0~2.0 parts of zinc acetate, 1.0~2.0 parts of frerrous chloride, 2.0~3.0 parts Lithium sulfate, 12.0~14.0 parts of Pyromellitic Acid and 10.0~15.0 parts of lithium hydroxide.
- 2. the zinc ion doping iron content coordination polymer according to claim 1 with excellent electrochemical performance, its feature It is：The polymer is the polymer of the excellent electrochemical performance shown in lithium ion battery.
- 3. the method for the doping iron content coordination polymer of the zinc ion with excellent electrochemical performance described in claim 1 is prepared, It is characterized in that：This method is as follows：The preparation of the polymer and its compound derivative is using simple hydrothermal synthesis method and then Annealing process, specially by 1.0~2.0 parts of zinc acetate, 1.0~2.0 parts of frerrous chloride, 2.0~3.0 parts of sulfuric acid Lithium, 12.0~14.0 parts of Pyromellitic Acid and 10.0~15.0 parts of lithium hydroxide are dissolved in 8~15ml water, magnetic agitation It is placed in after half an hour in the reactor of the polytetrafluoroethyllining lining of 15-50ml capacity, reactor is sealed and is maintained at temperature Section is that 24-72 hour hydrothermal synthesis reactions are carried out at 120-180 DEG C, then naturally cools to 0 DEG C -35 DEG C, precursor is filtered Go out, wash the solid particle for several times, being then collected into respectively with absolute ethyl alcohol and distilled water and be dried overnight at room temperature or 60 DEG C.
- 4. the preparation side of the zinc ion doping iron content coordination polymer according to claim 3 with excellent electrochemical performance Method, it is characterised in that：At 400-600 DEG C, dried precursor is heat-treated, 3- is kept in air atmosphere Obtain carbon composite oxides within 6 hours；Or constant temperature 3-6 hours obtain carbon coating oxidation in nitrogen atmosphere of the concentration more than 99.9% Thing composite.
- 5. the preparation side of the zinc ion doping iron content coordination polymer according to claim 3 with excellent electrochemical performance Method, it is characterised in that：Metal coordinating polymer precursor add be not more than precursor quality 10% graphene carry out ultrasound and Milled processed, obtain graphene coated metal coordinating polymer composite.
- 6. the preparation side of the zinc ion doping iron content coordination polymer according to claim 5 with excellent electrochemical performance Method, it is characterised in that：The graphene for adding not more than 10% carries out ultrasound and milled processed, obtains graphene coated metal-complexing Polymer, and it is heat-treated at 400-600 DEG C, kept for 3-6 hours obtain graphene and carbon bag in air atmosphere The compound of oxide is covered, i.e. graphene/carbon/zinc oxide/ferroso-ferric oxide.
- 7. the doping iron content polycomplexation of the zinc ion with excellent electrochemical performance according to any one in claim 3-6 The preparation method of compound, it is characterised in that：First filtered after precursor is filtered out using accumulative 10~50 milliliters of washings of absolute ethyl alcohol Spirit solvent, then reuse accumulative 30~60 milliliters of distillation water washing for several times.
- 8. the preparation side of the zinc ion doping iron content coordination polymer according to claim 7 with excellent electrochemical performance Method, it is characterised in that：Absolute ethyl alcohol concentration is 96%~100%, and room temperature is 0 DEG C -25 DEG C.
- 9. the preparation side of the zinc ion doping iron content coordination polymer according to claim 3 with excellent electrochemical performance Method, it is characterised in that：Carbon composite oxides are carbon/zinc oxide/ferroso-ferric oxide, and carbon coating oxide is carbon/zinc ferrite.
- 10. zinc ion doping iron content coordination polymer and its derivative with excellent electrochemical performance as claimed in claim 1 Thing material applications, it is characterised in that：It is applied in lithium ion battery.
- 11. purposes according to claim 10, it is characterised in that：Shown in lithium ion battery high specific capacity and Good cycle performance.
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