CN105932291B - A kind of method and application preparing porous carbon materials using metal organic frame as template - Google Patents
A kind of method and application preparing porous carbon materials using metal organic frame as template Download PDFInfo
- Publication number
- CN105932291B CN105932291B CN201610415509.1A CN201610415509A CN105932291B CN 105932291 B CN105932291 B CN 105932291B CN 201610415509 A CN201610415509 A CN 201610415509A CN 105932291 B CN105932291 B CN 105932291B
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- carbon materials
- materials
- template
- metal organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- 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
The invention discloses a kind of method and application preparing porous carbon materials using metal organic frame as template, the preparation method of the porous carbon materials includes the following steps：(1) organic ligand 5 (4 pyridine, 4 base benzamido) M-phthalic acid (H is synthesized2PYBI)；(2) Zn MOF materials are synthesized：Weigh Zn (NO3)2·6H2O and H2After PYBI is dissolved in solvent, reaction is heated in reaction kettle, room temperature is down to after reaction, obtains Zn MOF materials；(3) porous carbon materials are synthesized：The Zn MOF materials obtained using in step (2) are calcined under atmosphere of inert gases as presoma and obtain porous carbon materials.Compared with the existing technology, the present invention synthesizes Zn MOF materials using nitrogen heterocyclic ring carboxylic acids ligand, and uniformity of the porous carbon materials as lithium cell negative pole material nitrogen doped is prepared after fully ensuring that calcining；While ensureing to improve negative material specific capacity, its cyclical stability is further increased.
Description
Technical field
The present invention relates to the application fields of lithium ion battery negative material, more particularly to one kind is using metal organic frame as mould
Plate prepares method and the application of porous carbon materials.
Background technology
From after the generation of first time energy crisis, demand of the people to the mobile energy is continuously increased, this is excited to novel
The research of power supply system.To in the 1990s, scientist develops lithium-ion electric on the basis of lithium secondary battery is studied
Pond, and achieve breakthrough progress.Since lithium ion battery has good cycle, voltage is compared with high, energy density is big
The advantages that, so that it is rapidly become the secondary cell of the new generation of green high energy after Ni-MH battery.By the developmental research of last decade,
Currently, lithium ion battery has the larger market share in secondary cell market, and it is widely applied in daily life
Portable electronic product (such as：Computer, mobile phone, camera etc.) with the equipment such as electric bicycle, automobile.Lithium ion battery uses
The stratiform of lithium ion or the material of tunnel structure can be freely embeddable and deviate from as electrode material, just extremely stratiform
LiCoO2, and cathode then uses graphite material, and with non-aqueous lithium ion conducting medium, that is, the organic solvent for being dissolved with lithium salts is made
For electrolyte.When charging, lithium ion from anode deviate from after embedded cathode, when electric discharge, lithium ion escapes embedded anode from cathode again,
To form the two-way process of embedded abjection between electrode material.Compared to the operation principle of lithium secondary battery, due to lithium ion
Battery only passes through Li in charge and discharge process+Insertion in active electrode material and abjection, therefore lithium metal can be overcome molten
The shortcomings that going out with reduction and the formation of dendrite arm lithium, makes its safety enhance.Meanwhile to possess operating voltage higher (big for lithium ion battery
About 3.6V), it is small portable the advantages that, so that it is widely used in the electronic device.
Currently, the negative material of lithium ion battery mainly has carbon material, metal oxide, alloy type negative material etc.,
In due to carbon material have rich reserves, stable structure and lower-price characteristic, the research using it as negative material is the most
It is ripe.Carbon material includes graphite, hard carbon and soft carbon etc., and lithium ion battery is mainly applied to using graphite as negative material.Graphite
Material has good layer structure and electric conductivity, and the insertion reaction of lithium ion can occur when compared with low potential, be it is a kind of compared with
Good lithium ion insertion-deintercalation material, theoretical specific capacity 372mAh/g.Although graphite has preferable chemical property,
But by also more prominent the problems caused by its fault of construction, such as larger graphite layers are away from easy ting produce lithium ion and solvent
The embedding phenomenon altogether of molecule, organic solvent are easy to decompose, and loose porous solid electrolyte film (SEI films) is formed in electrode surface,
To reduce the coulombic efficiency of first charge-discharge.In addition, when graphite layers away from it is smaller when, with Li+Insertion repeatedly and abjection,
Graphite-structure is caused constantly to expand and shrink repeatedly so that graphite flake layer is easy to fall off and generates electrode material capacity and decline rapidly
Subtract.
Compared with carbon material, alloy type negative material has high theoretical specific capacity, good heat conductivity and prevents solvent embedding altogether
The advantages that entering, this makes the research of alloy type negative material obtain greatly concern.Alloy material includes mainly：Tinbase, antimony base,
Silicon substrate and germanium Base Metal etc., storage lithium are in the nature that metal, alloy or compound are reacted with Li generation alloyings and removal alloying, by
Usually there is larger lithium storage content in these alloy materials, therefore its theoretical specific capacity is generally higher, can reach carbon material
2-3 times.However, one apparent disadvantage of alloy material generally existing：In battery charge and discharge process, lithium ion it is repeatedly embedding
The large change of material structure and volume can be brought by entering and deviating from, and cause battery capacity rapid decay, to constrain alloy type
The process of Materials Commercial.
Metal oxide is a kind of novel lithium ion battery negative material, storage lithium mechanism and carbon material and alloy type material
Expect different, redox reaction or conversion reaction, realization cathode material occur in charge and discharge using metal oxide and Li
The storage lithium of material and de- lithium process.The theoretical specific capacity of metal oxide is generally higher, such as 3d transition metal oxides (CuO,
CoO and Mn3O4) theoretical specific capacity can reach 700mAh/g or more, this is provided to meet the research of the lithium ion battery of high power capacity
Good negative material.However, metal oxide generally existing cyclical stability is poor, high rate performance is low and charging/discharging voltage is stagnant
Afterwards the shortcomings of, therefore to improve the practicability of the material, effective method of modifying can be used and prepare nanostructure, pore structure and spy
Different pattern metal oxide.(Xu X,Cao R,Jeong S,et al.Spindle-like mesoporousα-Fe2O3anode
material prepared from MOF template for high-rate lithium batteries[J].Nano
letters,2012,12(9):4988-4991.)
Although lithium ion battery has been widely used for the electronic equipment of daily life, but itself aspect still has many
The shortcomings that.Lithium ion battery electrode material easy tos produce structural collapse and Volumetric expansion in charge and discharge process, this is caused
Phenomena such as battery capacity decaying and reduced service life.In order to overcome the decline of electrode material conductivity and body in charge and discharge process
The problems such as product expansion, can be used and conduct electricity very well and have the material of porous structure as electrode material.
Metal organic frame is a kind of containing carbon source (organic ligand) and source metal (metal ion) and with periodical net
The porous coordination of network structure has preferable storage characteristics since it is with porous structure and certain electric conductivity to lithium ion
Can, therefore lithium ion battery can be applied to directly as electrode material.But so far, with MOFs materials directly as electrode
Lithium ion battery have the shortcomings that smaller (Lin Y, Zhang Q, Zhao C, the et al.An exceptionally of specific capacity
stable functionalized metal–organic framework for lithium storage[J].Chemical
Communications, 2015,51 (4):697-699.).
Invention content
It is an object of the invention to overcome shortcoming and defect in the prior art, one kind is provided using metal organic frame as mould
Plate prepares method and the application of porous carbon materials.
The present invention is achieved by the following technical solutions：One kind preparing porous carbon materials by template of metal organic frame
Method and application, include the following steps：
(1) organic ligand 5- (4- pyridin-4-yls-benzamido)-M-phthalic acid (H is synthesized2PYBI)；
(2) Zn-MOF materials are synthesized：Weigh Zn (NO3)2·6H2O and H2After PYBI is dissolved in solvent, in reaction kettle
Heating reaction, is down to room temperature, obtains Zn-MOF materials after reaction；
(3) porous carbon materials are synthesized：The Zn-MOF materials obtained using in step (2) are as presoma, in inert gas atmosphere
It encloses lower calcining and obtains porous carbon materials.
Compared with the existing technology, the present invention synthesizes Zn-MOF materials using nitrogen heterocyclic ring carboxylic acids ligand, fully ensures that
Uniformity of the porous carbon materials being prepared after calcining as lithium cell negative pole material nitrogen doped；Ensureing to improve cathode material
While expecting specific capacity, its cyclical stability is further increased.
Further, in step (2), Zn (NO3)2·6H2O and H2The molar ratio of PYBI is 2:1-1:2.
Further, in step (2), Zn (NO3)2·6H2O and H2The molar ratio of PYBI is 2:1.
Further, in step (2), the solvent is that volume ratio is 1:1 DMF and the mixed solvent of water.
Further, in step (1), 4- bromopyridine hydrochlorides, 4- Carboxybenzeneboronic acids and sodium carbonate is weighed and is added in toluene, is added
Enter four triphenyl phosphorus palladiums and make catalyst, reaction 6-14h obtains intermediate product；Intermediate product is dried, it is anti-that thionyl chloride reflux is added
Ying Hou is evaporated excess of solvent, obtains solid；Solid is mixed with 5- amino isophthalic acids in DMF, 1-6h is reacted at room temperature,
Reaction solution is added into excessive distilled water, solid product, as H is precipitated2PYBI organic ligands.
Further, in the step (1), the molar ratio of 4- bromopyridine hydrochlorides, 4- Carboxybenzeneboronic acids and sodium carbonate is preferred
1:1:(0.28-0.43), the molar ratio preferably 0.002 of four triphenyl phosphorus palladium of catalyst and 4- bromopyridine hydrochlorides:1；The step
Suddenly in (1), it is 80 DEG C that thionyl chloride reflux temperature, which is added,.
Further, heating temperature is 40-80 DEG C in the step (2), reaction time 20-28h.
Further, in the step (3), the Zn-MOF materials obtained using in step (2) are as presoma, in nitrogen atmosphere
Under, calcine 6h in 900 DEG C.
The present invention also provides a kind of preparation methods of lithium battery, include the following steps：By porous carbon materials, binder,
Conductive black mixes in proportion, is tuned into pulpous state with solvent, is coated on copper foil, and vacuum drying is sliced after roll-in, obtains circular electrode
Piece；Electrode slice, diaphragm material, electrolyte are assembled into lithium ion battery.The porous carbon materials are the above-mentioned arbitrary side referred to
The porous carbon materials that method is prepared.
Compared with the existing technology, the lithium-ion electric that porous carbon materials using the present invention are prepared as negative material
Pond, coulombic efficiency is high, has high charge-discharge specific capacity, good high rate performance and cycle performance.
Further, the binder is Kynoar, and the conductive black is conductive acetylene carbon black, and the solvent is N-
Methyl pyrrolidone；The porous carbon materials, binder, conductive black mass ratio be 8:1:1.
In order to better understand and implement, the invention will now be described in detail with reference to the accompanying drawings.
Description of the drawings
Fig. 1 is the synthetic reaction step schematic diagram of the organic ligand of the present invention；
Fig. 2 be the present invention Zn-MOF materials in metallic zinc coordination context diagram；
Fig. 3 is the 3-D frame diagrams of the Zn-MOF materials of the present invention；
Fig. 4 is the cube network figure of the Zn-MOF materials of the present invention；
Fig. 5 is the PXRD figures of the porous carbon materials of the present invention；
Fig. 6 is the cycle performance test chart of the lithium ion battery prepared using the porous carbon materials of the present invention；
Fig. 7 is the cyclic voltammetry figure of the lithium ion battery prepared using the porous carbon materials of the present invention；
Fig. 8 is the constant current charge-discharge curve graph of the lithium ion battery prepared using the porous carbon materials of the present invention.
Specific implementation mode
It is of the invention to reach the technological means and its technique effect that predetermined goal of the invention is taken further to illustrate, with
Under in conjunction with the embodiments and attached drawing, to a kind of method preparing porous carbon materials as template using metal organic frame proposed by the present invention
And the specific implementation mode of application illustrates, detailed description are as follows.
A kind of method and application preparing porous carbon materials using metal organic frame as template of the present invention, including following step
Suddenly：
(1) organic ligand 5- (4- pyridin-4-yls-benzamido)-M-phthalic acid (H is synthesized2PYBI)：Weigh 4- bromines
Pyridine hydrochloride, 4- Carboxybenzeneboronic acids and sodium carbonate are added in toluene, and four triphenyl phosphorus palladiums are added and make catalyst, react 6-14h
Obtain intermediate product；Intermediate product is dried, after thionyl chloride back flow reaction is added, excess of solvent is evaporated, obtains solid；By solid
It is mixed in DMF with 5- amino isophthalic acids, reacts at room temperature 1-6h, reaction solution is added into excessive distilled water, be precipitated
Solid product, as H2PYBI organic ligands.
(2) Zn-MOF materials are synthesized：Weigh Zn (NO3)2·6H2O and H2After PYBI is dissolved in solvent, in reaction kettle
Heating reaction, is down to room temperature, obtains Zn-MOF materials after reaction.
(3) porous carbon materials are synthesized：The Zn-MOF materials obtained using in step (2) are as presoma, in inert gas atmosphere
It encloses lower calcining and obtains porous carbon materials.
In step (1) of the present invention, the molar ratio preferably 1 of 4- bromopyridine hydrochlorides, 4- Carboxybenzeneboronic acids and sodium carbonate:1:
(0.28-0.43), the molar ratio preferably 0.002 of four triphenyl phosphorus palladium of catalyst and 4- bromopyridine hydrochlorides:1.Protochloride is added
Sulfone reflux temperature is 80 DEG C.
In step (2) of the present invention, Zn (NO3)2·6H2O and H2The molar ratio of PYBI is 2:1-1:2, wherein Zn (NO3)2·
6H2O and H2The molar ratio of PYBI preferably 2:1.Heating temperature is preferably a certain temperature in 40-80 DEG C in step (2), reacts 20-
After 28h, then it is reduced to room temperature.It is 1 that solvent in step (2), which is volume ratio,:1 DMF and the mixed solvent of water.
In step (3) of the present invention, the calcination condition of Zn-MOF materials preferably calcines 6h at 900 DEG C.
The present invention also provides a kind of preparation methods of lithium battery, in proportion by porous carbon materials, binder, conductive black
Mixing, is tuned into pulpous state with solvent, is coated on copper foil, is dried in vacuo, is sliced after roll-in, obtains circular electric pole piece；By electrode slice, every
Membrane material, electrolyte are assembled into lithium ion battery.The porous carbon materials are the porous carbon materials that aforementioned preparation process obtains.
In the present invention, the preferred conductive acetylene carbon black of the conductive black, the binder are Kynoar.It is described more
The mass ratio preferably 8 of hole carbon material, binder, conductive black:1:1.The solvent is N-Methyl pyrrolidone.The vacuum is dry
Dry condition is：The first dry 0.5-3h in 60-90 DEG C of baking oven, then in 110-130 DEG C of dry 8- in vacuum drying chamber
12h.The diaphragm material is polyethylene.The electrolyte is the lithium hexafluoro phosphate (LiPF containing 1mol/L6) it is electrolyte, volume
Than ethylene carbonate (EC):Diethyl carbonate (DEC):Methyl ethyl carbonate (EMC)=1:1:1 is the electrolyte of solvent.
Embodiment 1
The method for preparing porous carbon materials as template using metal organic frame is described in detail in the present embodiment.
A method of porous carbon materials being prepared by template of metal organic frame, are included the following steps：
(1) 5- (4- pyridin-4-yls-benzamido)-M-phthalic acid (H is synthesized2PYBI)
Referring to Fig. 1, it is the synthetic reaction step schematic diagram of the organic ligand in the present invention.It weighs respectively
The sodium carbonate of the 4- bromopyridine hydrochlorides of 35.144mmol, the 4- Carboxybenzeneboronic acids of 35.144mmol and 10mmol is added to toluene
In solution, the four triphenyl phosphorus palladiums of 0.08mmol are added, four triphenyl phosphorus palladium of catalyst effect under, reaction 10h obtain it is white in
Between product.Intermediate product is dried, thionyl chloride is added, flows back at 80 DEG C, excess of solvent is evaporated after the completion of reaction, obtains Huang
Color solid.Yellow solid is mixed with 5- amino isophthalic acids in DMF, 3h is reacted at room temperature, reaction solution is added to
In the distilled water of 500mL, a large amount of solids, as H are precipitated2PYBI ligands.
(2) Zn-MOF materials are synthesized
Weigh the Zn (NO of 0.1mmol3)2·6H2The H of O and 0.05mmol2The volume ratio that PYBI is dissolved in 6mL is 1:1
DMF and H2After O in the mixed solvents, in the reaction kettle that liner is polytetrafluoroethylene (PTFE) material, at 80 DEG C after heating reaction for 24 hours, drop
To room temperature, Zn-MOF materials are obtained.
(3) the Zn-MOF materials obtained using in step (2) are as presoma, in a nitrogen atmosphere, calcine 6h in 900 DEG C and obtain
To porous carbon materials.
The present embodiment additionally provides a kind of method preparing lithium ion battery using the porous carbon materials.Specifically, will
Porous carbon materials, Kynoar, conductive acetylene carbon black in mass ratio 8:1:1 mixing, is solvent tune with N-Methyl pyrrolidone
Pulp is coated on copper foil, first the dry 1h in 80 DEG C of baking oven, then in 120 DEG C of dry 10h in vacuum drying chamber.Roller
It is sliced after pressure, obtains circular electric pole piece.By electrode slice, polyethylene diagrams material, electrolyte is the LiPF of 1mol/L6, solvent be
Volume ratio is 1:1:The electrolyte of the mixed solution of 1 EC, DEC and EMC is assembled into lithium ion battery.It is described in the present embodiment
Lithium ion battery is the button cell of model 2032, but not limited to this.
Embodiment 2
In the present embodiment, a method of porous carbon materials being prepared by template of metal organic frame, are included the following steps：
(1) 5- (4- pyridin-4-yls-benzamido)-M-phthalic acid (H is synthesized2PYBI)
Referring to Fig. 1, it is the synthetic reaction step schematic diagram of the organic ligand in the present invention.It weighs respectively
The sodium carbonate of the 4- bromopyridine hydrochlorides of 35.144mmol, the 4- Carboxybenzeneboronic acids of 35.144mmol and 10.5mmol is added to first
In benzole soln, the four triphenyl phosphorus palladiums of 0.08mmol are added, under the effect of four triphenyl phosphorus palladium of catalyst, reaction 14h obtains white
Intermediate product.Intermediate product is dried, thionyl chloride is added, flows back at 80 DEG C, excess of solvent is evaporated after the completion of reaction, obtains
Yellow solid.Yellow solid is mixed with 5- amino isophthalic acids in DMF, 1h is reacted at room temperature, reaction solution is added to
In the distilled water of 500mL, a large amount of solids, as H are precipitated2PYBI organic ligands.
(2) Zn-MOF materials are synthesized
Weigh the Zn (NO of 0.3mmol3)2·6H2The H of O and 0.2mmol2The volume ratio that PYBI is dissolved in 6mL is 1:1
DMF and H2After O in the mixed solvents, in the reaction kettle that liner is polytetrafluoroethylene (PTFE) material, at 40 DEG C after heating reaction 28h, drop
To room temperature, Zn-MOF materials are obtained.
(3) the Zn-MOF materials obtained using in step (2) are as presoma, in a nitrogen atmosphere, calcine 8h in 900 DEG C and obtain
To porous carbon materials.
The present embodiment additionally provides a kind of method preparing lithium ion battery using the porous carbon materials.Specifically, will
Porous carbon materials, Kynoar, conductive acetylene carbon black in mass ratio 8:1:1 mixing, is solvent tune with N-Methyl pyrrolidone
Pulp is coated on copper foil, first the dry 3h in 60 DEG C of baking oven, then in 110 DEG C of dry 12h in vacuum drying chamber.Roller
It is sliced after pressure, obtains circular electric pole piece.By electrode slice, polyethylene diagrams material, electrolyte is the LiPF of 1mol/L6, solvent be
Volume ratio is 1:1:The electrolyte of the mixed solution of 1 EC, DEC and EMC is assembled into lithium ion battery.It is described in the present embodiment
Lithium ion battery is the button cell of model 2032, but not limited to this.
Embodiment 3
In the present embodiment, a method of porous carbon materials being prepared by template of metal organic frame, are included the following steps：
(1) 5- (4- pyridin-4-yls-benzamido)-M-phthalic acid (H is synthesized2PYBI)
Referring to Fig. 1, it is the synthetic reaction step schematic diagram of the organic ligand in the present invention.It weighs respectively
The sodium carbonate of the 4- bromopyridine hydrochlorides of 35.144mmol, the 4- Carboxybenzeneboronic acids of 35.144mmol and 15mmol is added to toluene
In solution, the four triphenyl phosphorus palladiums of 0.08mmol are added, under the effect of four triphenyl phosphorus palladium of catalyst, reaction 6h obtains white centre
Product.Intermediate product is dried, thionyl chloride is added, flows back at 80 DEG C, excess of solvent is evaporated after the completion of reaction, obtains yellow
Solid.Yellow solid is mixed with 5- amino isophthalic acids in DMF, 6h is reacted at room temperature, reaction solution is added to 500mL
Distilled water in, a large amount of solids, as H are precipitated2PYBI organic ligands.
(2) Zn-MOF materials are synthesized
Weigh the Zn (NO of 0.1mmol3)2·6H2The H of O and 0.2mmol2The volume ratio that PYBI is dissolved in 6mL is 1:1
DMF and H2After O in the mixed solvents, in the reaction kettle that liner is polytetrafluoroethylene (PTFE) material, at 60 DEG C after heating reaction 20h, drop
To room temperature, Zn-MOF materials are obtained.
(3) the Zn-MOF materials obtained using in step (2) are as presoma, in a nitrogen atmosphere, calcine 7h in 900 DEG C and obtain
To porous carbon materials.
The present embodiment additionally provides a kind of method preparing lithium ion battery using the porous carbon materials.Specifically, will
Porous carbon materials, Kynoar, conductive acetylene carbon black in mass ratio 8:1:1 mixing, is solvent tune with N-Methyl pyrrolidone
Pulp is coated on copper foil, first the dry 0.5h in 90 DEG C of baking oven, then in 130 DEG C of dry 8h in vacuum drying chamber.Roller
It is sliced after pressure, obtains circular electric pole piece.By electrode slice, polyethylene diagrams material, electrolyte is the LiPF of 1mol/L6, solvent be
Volume ratio is 1:1:The electrolyte of the mixed solution of 1 EC, DEC and EMC is assembled into lithium ion battery.It is described in the present embodiment
Lithium ion battery is the button cell of model 2032, but not limited to this.
Effect example
Please refer to Fig. 2-4, be respectively the present invention Zn-MOF materials in the coordination context diagram of metallic zinc and porous
The 3-D frame diagrams of carbon material Zn-MOF.As can be known from Fig. 2, metallic zinc is respectively from H using 6 coordinations in Zn-MOF2PYBI
The nitrogen-atoms on the oxygen atom and pyridine on carboxyl in ligand.Fig. 3 illustrates Zn-MOF materials there are prodigious hole, in conjunction with
Fig. 4 show the Zn-MOF materials three dimensions by paddle wheel formula connection show it is regularly arranged.
The Zn-MOF materials are calcined under 900 DEG C of nitrogen atmospheres and obtain porous carbon materials.Referring to Fig. 5, it is this
The PXRD figures of porous carbon materials in inventive embodiments 1.It can be seen that only two characteristic peaks of carbon material, it was demonstrated that the material
Material is carbon material.
Referring to Fig. 6, it is the cycle performance test chart of the lithium ion battery prepared using the porous carbon materials of the present invention.
It can be seen that the lithium ion battery that the porous carbon materials are prepared as negative material, shows good charge-discharge performance,
Electric discharge can reach 2157mAh/g for the first time, and by the cycle of 100 charge and discharge, specific capacity can be stablized in 1104mAh/g or so,
Its coulombic efficiency is higher, shows good chemical property.
Referring to Fig. 7, it is the cyclic voltammetry figure of the lithium ion battery prepared using the porous carbon materials of the present invention.
It can be seen from the figure that, there are one redox peaks in first run test, and this peak disappears in second and third wheel, this end
In an irreversible process, i.e., form SEI films in electrode surface.SEI films have organic solvent insoluble, can be in Organic Electricity
It is stabilized in solution liquid, so as to effectively organize the subsequent total insertion of solvent, avoids destructiveness of the solvent molecule to electrode
It influences, to improve the service life of battery.
Referring to Fig. 8, it is the constant current charge-discharge curve of the lithium ion battery prepared using the porous carbon materials of the present invention
Figure.It can be seen that the charge and discharge platform for the lithium ion battery that the porous carbon materials are prepared as negative material is in 1V
Hereinafter, having relatively low charge and discharge platform, illustrate that the porous carbon materials are well suited as the cathode material of lithium ion battery
Material.
Compared with the existing technology, the present invention synthesizes Zn-MOF materials using nitrogen heterocyclic ring carboxylic acids ligand, fully ensures that
The uniformity for the lithium cell negative pole material nitrogen doped being prepared after calcining；Ensureing to improve the same of negative material specific capacity
When, further increase its cyclical stability.The porous carbon materials are applied to lithium ion battery by the present invention
In, first discharge specific capacity 2157mAh/g, when charging and discharging currents density is 100mA/g, specific capacity after recycling 100 times
Stablize in 1104mAh/g, there is good cycle performance.Also, when porous carbon materials of the present invention are as negative material,
Negative material structure, specific surface area are adjustable, the raising of negative material chemical property easy to implement；Metal organic framework compound
Structure and specific surface area it is adjustable, realize the porous carbon materials that calcining is prepared by selecting different calcination temperature
The regulation and control of structure, and then be easy optimization and obtain high performance lithium cell cathode material.
The invention is not limited in the above embodiments, if the various changes or deformation to the present invention do not depart from the present invention
Spirit and scope, if these changes and deformation belong within the scope of the claim and equivalent technologies of the present invention, then this hair
It is bright to be also intended to comprising these changes and deformation.
Claims (10)
1. a kind of method and application preparing porous carbon materials using metal organic frame as template, it is characterised in that：Including following
Step：
(1) organic ligand 5- (4- pyridin-4-yls-benzamido)-M-phthalic acid (H is synthesized2PYBI)；
(2) Zn-MOF materials are synthesized：Weigh Zn (NO3)2·6H2O and H2After PYBI is dissolved in solvent, heated in reaction kettle anti-
It answers, is down to room temperature after reaction, obtain Zn-MOF materials；
(3) porous carbon materials are synthesized：The Zn-MOF materials obtained using in step (2) are as presoma, under atmosphere of inert gases
Calcining obtains porous carbon materials.
2. the method according to claim 1 for preparing porous carbon materials as template using metal organic frame, it is characterised in that：
In step (2), Zn (NO3)2·6H2O and H2The molar ratio of PYBI is 2:1-1:2.
3. the method according to claim 2 for preparing porous carbon materials as template using metal organic frame, it is characterised in that：
In step (2), Zn (NO3)2·6H2O and H2The molar ratio of PYBI is 2:1.
4. preparing porous carbon materials by template of metal organic frame according to any claim in claim 1-3
Method, it is characterised in that：In step (2), the solvent is that volume ratio is 1:1 DMF and the mixed solvent of water.
5. the method according to claim 1 for preparing porous carbon materials as template using metal organic frame, it is characterised in that：
In step (1), weighs 4- bromopyridine hydrochlorides, 4- Carboxybenzeneboronic acids and sodium carbonate and be added in toluene, four triphenyl phosphorus palladiums are added
Make catalyst, reaction 6-14h obtains intermediate product；Intermediate product is dried, after thionyl chloride back flow reaction is added, is evaporated extra molten
Agent obtains solid；Solid is mixed with 5- amino isophthalic acids in DMF, 1-6h is reacted at room temperature, reaction solution is added to mistake
In the distilled water of amount, solid product, as H is precipitated2PYBI organic ligands.
6. the method according to claim 5 for preparing porous carbon materials as template using metal organic frame, it is characterised in that：
In the step (1), the molar ratio preferably 1 of 4- bromopyridine hydrochlorides, 4- Carboxybenzeneboronic acids and sodium carbonate:1:(0.28-0.43),
The molar ratio preferably 0.002 of four triphenyl phosphorus palladium of catalyst and 4- bromopyridine hydrochlorides:1；In the step (1), chlorination is added
Sulfoxide reflux temperature is 80 DEG C.
7. the method according to claim 4 for preparing porous carbon materials as template using metal organic frame, it is characterised in that：
Heating temperature is 40-80 DEG C in the step (2), reaction time 20-28h.
8. preparing porous carbon by template of metal organic frame according to any claim in claim 1-3 or 5-7
The method of material, it is characterised in that：In the step (3), the Zn-MOF materials that are obtained using in step (2) as presoma,
Under nitrogen atmosphere, 6h is calcined in 900 DEG C.
9. a kind of preparation method of lithium battery, it is characterised in that：Include the following steps：By porous carbon materials, binder, conductive charcoal
It is black to mix in proportion, it is tuned into pulpous state with solvent, is coated on copper foil, is dried in vacuo, is sliced after roll-in, obtains circular electric pole piece；It will
Electrode slice, diaphragm material, electrolyte are assembled into lithium ion battery；The porous carbon materials are any right in claim 1-8
It is required that the porous carbon materials that the preparation method is prepared.
10. the preparation method of lithium battery according to claim 9, it is characterised in that：The binder is Kynoar,
The conductive black is conductive acetylene carbon black, and the solvent is N-Methyl pyrrolidone；The porous carbon materials, are led at binder
The mass ratio of electric carbon black is 8:1:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610415509.1A CN105932291B (en) | 2016-06-14 | 2016-06-14 | A kind of method and application preparing porous carbon materials using metal organic frame as template |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610415509.1A CN105932291B (en) | 2016-06-14 | 2016-06-14 | A kind of method and application preparing porous carbon materials using metal organic frame as template |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105932291A CN105932291A (en) | 2016-09-07 |
| CN105932291B true CN105932291B (en) | 2018-08-07 |
Family
ID=56832824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610415509.1A Expired - Fee Related CN105932291B (en) | 2016-06-14 | 2016-06-14 | A kind of method and application preparing porous carbon materials using metal organic frame as template |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105932291B (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106477551A (en) * | 2016-10-13 | 2017-03-08 | 南京航空航天大学 | A kind of metal organic frame derives Nitrogen-rich porous carbon material and preparation method thereof |
| CN106328948B (en) * | 2016-10-27 | 2020-03-13 | 华南师范大学 | Based on [ Zn (BIBBA)2]nPreparation method of lithium battery negative electrode material |
| CN106450227B (en) * | 2016-11-24 | 2020-04-03 | 福建师范大学 | Method for preparing lithium battery by using In2O3/C composite material with hierarchical structure |
| CN107068947B (en) * | 2017-04-25 | 2021-01-22 | 中国石油大学(华东) | Modified diaphragm for lithium-sulfur battery and preparation method thereof |
| CN108394965A (en) * | 2017-12-26 | 2018-08-14 | 南开大学 | A method of it burning copper metal organic frame using nitrogen and makes anode material |
| CN108461306B (en) * | 2018-03-28 | 2019-07-12 | 浙江大学 | A kind of multi-layer N doped carbon nanometer rod composite material and preparation method thereof |
| CN110473710A (en) * | 2018-05-10 | 2019-11-19 | 北京化工大学 | Porous carbon materials and its preparation method and application |
| CN108807000B (en) * | 2018-07-09 | 2020-03-27 | 华南师范大学 | Preparation method of nano porous carbon for high-performance super capacitor |
| CN108735523B (en) * | 2018-07-17 | 2020-03-27 | 西北大学 | Preparation method and application of Zn-MOF (Zinc-organic framework) with window beam structure and carbon material derived from Zn-MOF |
| CN109390163B (en) * | 2018-10-29 | 2020-10-16 | 西北大学 | Preparation method of two-dimensional Cu-MOF-derived porous carbon nanosheet |
| CN109759110B (en) * | 2019-01-03 | 2022-04-22 | 华南理工大学 | Nitrogen-doped porous carbon loaded titanium dioxide photocatalyst and preparation method and application thereof |
| CN109824028A (en) * | 2019-01-18 | 2019-05-31 | 华南师范大学 | It is a kind of using coordination polymer as the nitrogen-doped porous carbon material of precursor preparation and application |
| CN109888238A (en) * | 2019-03-08 | 2019-06-14 | 湖南大学 | A kind of height ratio capacity, lithium ion battery negative material of high rate capability and preparation method thereof |
| CN110504450B (en) * | 2019-07-17 | 2022-08-12 | 温州大学新材料与产业技术研究院 | Preparation method of heteroatom-doped hierarchical pore carbon material and application of heteroatom-doped hierarchical pore carbon material in lithium battery negative electrode slurry |
| CN112499685B (en) * | 2020-11-26 | 2023-02-10 | 南昌航空大学 | Preparation of MnO 2 Method for preparing @ porous carbon composite wave-absorbing material |
| CN112885999A (en) * | 2021-01-04 | 2021-06-01 | 昆山宝创新能源科技有限公司 | Tin-based oxide negative electrode material and preparation method and application thereof |
| CN114904356B (en) * | 2021-02-08 | 2024-03-26 | 中国科学院大连化学物理研究所 | Method for separating nitrogen and oxygen |
| CN113249060B (en) * | 2021-05-11 | 2022-06-28 | 乌海瑞森新能源材料有限公司 | Preparation method of polyvinylidene fluoride modified by lithium ion battery binder |
| CN114744148A (en) * | 2022-04-01 | 2022-07-12 | 三峡大学 | Preparation method of hard carbon cathode of high-rate-performance sodium ion battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045116B (en) * | 2014-06-12 | 2016-01-27 | 江苏大学 | The preparation method of nano porous metal oxide/carbon lithium ion battery negative material |
-
2016
- 2016-06-14 CN CN201610415509.1A patent/CN105932291B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105932291A (en) | 2016-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105932291B (en) | A kind of method and application preparing porous carbon materials using metal organic frame as template | |
| CN105932285B (en) | It is a kind of using metal organic frame as the preparation method of the lithium cell cathode material of template | |
| CN104681797B (en) | A kind of preparation method of silicon-carbon composite cathode electrode, lithium ion battery | |
| CN102751501B (en) | A kind of triphenylamine derivative polymer is as the application of anode material for lithium-ion batteries | |
| CN102916195B (en) | Graphene-coated copper oxide composite cathode material and method for manufacturing same | |
| CN104868098B (en) | A kind of carbon composite Cu3P Cu negative electrode of lithium ion battery and preparation method thereof | |
| CN106920989B (en) | A kind of copper selenium compound is the sodium-ion battery of negative electrode material | |
| CN107634226B (en) | Synthesis and application of lithium ion battery cathode material taking coordination polymer as template | |
| CN109776423A (en) | A kind of double imidazole ring functional ion liquids and preparation method thereof and electrolyte and lithium secondary battery | |
| WO2017101849A1 (en) | Solid electrolyte, solid electrolyte membrane and manufacturing method therefor, and secondary battery | |
| CN106252663B (en) | Metal-organic framework materials CuBDC nanometer sheet and its preparation method and application | |
| CN103928668B (en) | Lithium ion battery and preparation method of anode material thereof | |
| CN104009215B (en) | A kind of vanadium dioxide-graphene complex and the purposes as anode material for lithium-ion batteries thereof | |
| CN103825014B (en) | A kind of preparation method of high-voltage anode material of lithium ion batteries lithium nickel manganese composite oxide | |
| CN108054350A (en) | Lithium-sulfur battery composite cathode material and preparation method thereof | |
| CN110416551A (en) | Cathode for lithium rechargeable battery and the lithium rechargeable battery including it | |
| CN110600699B (en) | Preparation method of three-dimensional ordered mesoporous MOF material | |
| CN105789561B (en) | A kind of preparation method of lithium-polysulfide secondary cell | |
| CN107946564A (en) | Rich sodium manganese base Na4Mn2O5/Na0.7MnO2Composite material and its preparation method and application | |
| CN102683698B (en) | Preparation method of conductive modified lithium iron phosphate | |
| CN103560280B (en) | The chemical synthesizing method of lithium ion battery | |
| CN113336897B (en) | Metal-organic framework-based material for in-hole confined polymerization of organic monomer, and preparation method and application thereof | |
| CN103943856B (en) | A kind of preparation method of phthalocyanine-iron phosphate compound anode material of lithium | |
| CN110098401B (en) | Preparation method, product and application of lithium titanate/poly-3, 4-ethylenedioxythiophene | |
| CN110247041A (en) | A kind of ZnNiO/C composite nano materials and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180807 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |