CN105932291A - Method for preparing porous carbon material by taking metal organic framework as template, and application thereof - Google Patents
Method for preparing porous carbon material by taking metal organic framework as template, and application thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing a porous carbon material by taking a metal organic framework as a template, and an application thereof. The preparation method for the porous carbon material comprises the following steps of (1) synthesizing an organic ligand 5-(4-pyridine-4-yl-benzamido)-isophthalic acid (H<2>PYBI); (2) synthesizing a Zn-MOF material: weighing Zn(NO<3>)<2>.6H<2>O and H<2>PYBI and dissolving into a solvent, carrying out a heating reaction in a reaction kettle, and then cooling to the room temperature after the reaction is completed to obtain the Zn-MOF material; (3) synthesizing the porous carbon material: taking the Zn-MOF material obtained in the step (2) as the precursor, and calcining the precursor under an inert gas atmosphere to obtain the porous carbon material. Compared with the prior art, a nitrogen-contained heterocyclic ring carboxylic acid ligand is adopted to synthesize the Zn-MOF material; and then the Zn-MOF material is fully calcined to prepare the porous carbon material; when the porous carbon material is used as the negative electrode of the lithium battery, the uniformity of the doped nitrogen element is realized; and it is ensured that the specific capacity of the negative electrode is improved while the cycling stability is further improved.
Description
Technical field
The present invention relates to the application of lithium ion battery negative material, particularly relate to one and prepare for template with metal organic frame
The method of porous carbon materials and application.
Background technology
After first time energy crisis occurs, the demand of the mobile energy is continuously increased by people, and this excites novel power supply body
The research of system.To the nineties in 20th century, scientist develops lithium ion battery on the basis of lithium secondary battery is studied, and
Achieve breakthrough progress.Due to advantages such as lithium ion battery have good cycle, and voltage is higher, energy density is big,
It is made to rapidly become the secondary cell of new generation of green high energy after Ni-MH battery.Through the developmental research of last decade, at present, lithium
Ion battery has had the bigger market share, and the portable electric being widely applied in daily life in secondary cell market
Sub-product (such as: computer, mobile phone, photographing unit etc.) and the equipment such as electric bicycle, automobile.Lithium ion battery uses can be certainly
By embedding and deviate from the stratiform of lithium ion or the material of the tunnel structure LiCoO as electrode material, the most extremely stratiform2, and negative pole
Then use graphite material, and with non-aqueous lithium ion conducting medium, be i.e. dissolved with the organic solvent of lithium salts as electrolyte.Charging
Time, lithium ion embeds negative pole after positive pole is deviate from, and during electric discharge, lithium ion embeds positive pole from negative pole effusion again, thus at electrode material
The two-way process embedding abjection is formed between material.Compared to the operation principle of lithium secondary battery, owing to lithium ion battery is in discharge and recharge
Journey is only passed through Li+Embedding in active electrode material and abjection, therefore can overcome lithium metal dissolution and reduction and dendrite arm lithium shape
The shortcoming become so that it is safety strengthens.Meanwhile, lithium ion battery has running voltage higher (about 3.6V), volume little Yi
The advantage such as carry so that it is be widely used in the electronic device.
At present, the negative material of lithium ion battery mainly has material with carbon element, metal-oxide, alloy type negative material etc., Qi Zhongyou
In material with carbon element, there is rich reserves, Stability Analysis of Structures and lower-price characteristic, the most ripe as the research of negative material using it.
Material with carbon element includes graphite, hard carbon and soft carbon etc., is mainly applied to lithium ion battery using graphite as negative material.Graphite material has
Have good layer structure and electric conductivity, the insertion reaction of lithium ion just can occur when relatively electronegative potential, be a kind of preferably lithium from
Son embedding-deintercalation material, its theoretical specific capacity is 372mAh/g.Although graphite has preferable chemical property, but is tied by it
Problem caused by structure defect is the most prominent, and the biggest graphite layers is away from easily producing the common embedding of lithium ion and solvent molecule
Phenomenon, organic solvent easily decomposes, and forms loose porous solid electrolyte film (SEI film) at electrode surface, thus reduces head
The coulombic efficiency of secondary discharge and recharge.Additionally, when graphite layers is when less, along with Li+Embedding repeatedly and abjection, cause graphite to be tied
Structure the most repeatedly expands and shrinks so that graphite flake layer easily comes off and produces electrode material capacity and decay rapidly.
Compared with material with carbon element, alloy type negative material has that theoretical specific capacity is high, good heat conductivity and prevent solvent embedding altogether etc. excellent
Point, this makes the research of alloy type negative material obtain concern greatly.Alloy type material specifically includes that tinbase, antimonio, silica-based
With germanio metal etc., its storage lithium is in the nature metal, alloy or complex and occurs alloying and removal alloying to react, due to this with Li
A little alloy type materials generally have bigger lithium storage content, and therefore its theoretical specific capacity is the highest, can reach 2-3 times of material with carbon element.
But, generally there is an obvious shortcoming in alloy type material: in battery charge and discharge process, the embedding repeatedly of lithium ion and de-
Go out the large change that can bring material structure and volume, cause battery capacity rapid decay, thus constrain alloy type material commodity
The process changed.
Metal-oxide is a kind of novel lithium ion battery negative material, and its storage lithium mechanism and material with carbon element and alloy type material are
Difference, utilizes metal-oxide and Li that redox reaction or conversion reaction occur when discharge and recharge, it is achieved the storage lithium of negative material
With de-lithium process.The theoretical specific capacity of metal-oxide is typically the highest, such as 3d transition metal oxide (CuO, CoO and
Mn3O4) theoretical specific capacity can reach more than 700mAh/g, this is that the research of the lithium ion battery meeting high power capacity provides
Good negative material.But, metal-oxide generally exists that cyclical stability is poor, high rate performance is low and charging/discharging voltage is delayed
Etc. shortcoming, therefore for improving the practicality of this material, effective method of modifying can be used to prepare nanostructured, pore structure and special
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 self aspect yet suffers from lacking of many
Point.In charge and discharge process, lithium ion battery electrode material easily produces structural collapse and Volumetric expansion, which results in battery
The phenomenons such as capacity attenuation and shortening in service life.In order to overcome electrode material conductivity in charge and discharge process to decline and volumetric expansion etc.
Problem, can use the material conducting electricity very well and having loose structure as electrode material.
Metal organic frame is that one contains carbon source (organic ligand) and source metal (metal ion) and has periodic network knot
The porous coordination of structure, owing to it has loose structure and certain electric conductivity, has preferable storge quality to lithium ion, because of
This can be applied to lithium ion battery directly as electrode material.But so far, with MOFs material directly as the lithium of electrode
There is the less shortcoming of specific capacity (Lin Y, Zhang Q, Zhao C, et al.An exceptionally stable in ion battery
Functionalized metal organic framework for lithium storage [J] .Chemical Communications, 2015,
51(4):697-699.)。
Summary of the invention
It is an object of the invention to overcome shortcoming and defect of the prior art, it is provided that one is prepared with metal organic frame for template
The method of porous carbon materials and application.
The present invention is achieved by the following technical solutions: a kind of method preparing porous carbon materials for template with metal organic frame
And application, comprise the following steps:
(1) synthesis organic ligand 5-(4-pyridin-4-yl-benzamido)-M-phthalic acid (H2PYBI)；
(2) synthesis Zn-MOF material: weigh Zn (NO3)2·6H2O and H2After PYBI is dissolved in solvent, in reactor
Reacting by heating, reaction is down to room temperature after terminating, is obtained Zn-MOF material；
(3) synthesizing porous material with carbon element: the Zn-MOF material obtained in step (2) is as presoma, at noble gas atmosphere
Enclose lower calcining and obtain porous carbon materials.
Relative to prior art, the present invention uses nitrogen heterocyclic ring carboxylic acids part to synthesize Zn-MOF material, fully ensures that calcining
After the porous carbon materials for preparing as the uniformity of lithium cell negative pole material nitrogen doped；Ensureing raising negative material specific volume
While amount, improve its cyclical stability further.
Further, in step (2), Zn (NO3)2·6H2O and H2The mol ratio of PYBI is 2:1-1:2.
Further, in step (2), Zn (NO3)2·6H2O and H2The mol ratio of PYBI is 2:1.
Further, in step (2), described solvent be volume ratio be DMF and the mixed solvent of water of 1:1.
Further, in step (1), weigh 4-bromopyridine hydrochloride, 4-Carboxybenzeneboronic acid and sodium carbonate and add in toluene, add
Four triphenyl phosphorus palladiums make catalyst, and reaction 6-14h obtains intermediate product；Dry intermediate product, add thionyl chloride back flow reaction
After, it is evaporated excess of solvent, obtains solid；Solid is mixed in DMF with 5-amino isophthalic acid, room temperature reaction 1-6h,
Reactant liquor is added to the distilled water of excess, separates out solid product, be H2PYBI organic ligand.
Further, in described step (1), the preferred 1:1 of mol ratio of 4-bromopyridine hydrochloride, 4-Carboxybenzeneboronic acid and sodium carbonate:
(0.28-0.43), catalyst four triphenyl phosphorus palladium and the preferred 0.002:1 of mol ratio of 4-bromopyridine hydrochloride；Described step (1)
In, adding thionyl chloride reflux temperature is 80 °.
Further, in described step (2), heating-up temperature is 40-80 °, and the response time is 20-28h.
Further, in described step (3), the Zn-MOF material obtained in step (2) is as presoma, in blanket of nitrogen
Under enclosing, calcine 6h in 900 °.
Present invention also offers the preparation method of a kind of lithium battery, comprise the following steps: by porous carbon materials, binding agent, conduction
White carbon black is mixed in proportion, and with solvent furnishing pulpous state, is coated on Copper Foil, vacuum drying, cuts into slices, obtain circular electric pole piece after roll-in；
Electrode slice, diaphragm material, electrolyte are assembled into lithium ion battery.Described porous carbon materials is the above-mentioned any means system mentioned
The standby porous carbon materials obtained.
Relative to prior art, use the lithium ion battery that the porous carbon materials of the present invention prepares, coulomb as negative material
Efficiency is high, has high charge-discharge specific capacity, good high rate performance and cycle performance.
Further, described binding agent is Kynoar, and described conductive black is conductive acetylene white carbon black, and described solvent is N-methyl
Ketopyrrolidine；Described porous carbon materials, binding agent, the mass ratio of conductive black are 8:1:1.
In order to be more fully understood that and implement, describe the present invention below in conjunction with the accompanying drawings in detail.
Accompanying drawing explanation
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 material in the coordination environment figure of metallic zinc；
Fig. 3 is the 3-D frame diagram of the Zn-MOF material of the present invention；
Fig. 4 is the cube network figure of the Zn-MOF material of the present invention；
Fig. 5 is the PXRD figure of the porous carbon materials of the present invention；
Fig. 6 is the cycle performance test figure of the lithium ion battery using the porous carbon materials of the present invention to prepare；
Fig. 7 is the cyclic voltammetry figure of the lithium ion battery using the porous carbon materials of the present invention to prepare；
Fig. 8 is the constant current charge-discharge curve chart of the lithium ion battery using the porous carbon materials of the present invention to prepare.
Detailed description of the invention
By further illustrate the present invention with the technological means reached predetermined goal of the invention and taked and technique effect thereof, below in conjunction with
Embodiment and accompanying drawing, propose the present invention a kind of prepares the method for porous carbon materials and application with metal organic frame for template
Detailed description of the invention illustrates, and describes in detail as follows.
A kind of method and application preparing porous carbon materials with metal organic frame for template of the present invention, comprises the following steps:
(1) synthesis organic ligand 5-(4-pyridin-4-yl-benzamido)-M-phthalic acid (H2PYBI): weigh 4-bromine pyrrole
Thiamine hydrochloride, 4-Carboxybenzeneboronic acid and sodium carbonate add in toluene, add four triphenyl phosphorus palladiums and make catalyst, and reaction 6-14h obtains
To intermediate product；Dry intermediate product, after adding thionyl chloride back flow reaction, be evaporated excess of solvent, obtain solid；By solid
Mix in DMF with 5-amino isophthalic acid, room temperature reaction 1-6h, reactant liquor is added to the distilled water of excess, analysis
Go out solid product, be H2PYBI organic ligand.
(2) synthesis Zn-MOF material: weigh Zn (NO3)2·6H2O and H2After PYBI is dissolved in solvent, in reactor
Reacting by heating, reaction is down to room temperature after terminating, is obtained Zn-MOF material.
(3) synthesizing porous material with carbon element: the Zn-MOF material obtained in step (2) is as presoma, at noble gas atmosphere
Enclose lower calcining and obtain porous carbon materials.
In step of the present invention (1), the preferred 1:1:(0.28-0.43 of mol ratio of 4-bromopyridine hydrochloride, 4-Carboxybenzeneboronic acid and sodium carbonate),
Catalyst four triphenyl phosphorus palladium and the preferred 0.002:1 of mol ratio of 4-bromopyridine hydrochloride.Adding thionyl chloride reflux temperature is 80 °.
In step of the present invention (2), Zn (NO3)2·6H2O and H2The mol ratio of PYBI is 2:1-1:2, wherein Zn (NO3)2·6H2O
And H2The preferred 2:1 of mol ratio of PYBI.In step (2), heating-up temperature is preferably 40-80 ° of interior a certain temperature, reacts 20-28
After h, then it is reduced to room temperature.Solvent in step (2) be volume ratio be DMF and the mixed solvent of water of 1:1.
In step of the present invention (3), the calcination condition of Zn-MOF material preferably calcines 6h under 900 °.
Present invention also offers the preparation method of a kind of lithium battery, porous carbon materials, binding agent, conductive black be mixed in proportion,
With solvent furnishing pulpous state, it is coated on Copper Foil, vacuum drying, cuts into slices after roll-in, obtain circular electric pole piece；By electrode slice, barrier film
Material, electrolyte are assembled into lithium ion battery.Described porous carbon materials is the porous carbon materials that aforementioned preparation process obtains.
In the present invention, described conductive black preferred conductive acetylene white carbon black, described binding agent is Kynoar.Described porous carbon
Material, binding agent, the preferred 8:1:1 of mass ratio of conductive black.Described solvent is N-Methyl pyrrolidone.Described vacuum drying
Condition is: be first dried 0.5-3h in the baking oven of 60-90 °, then in 110-130 ° of dry 8-12h in vacuum drying oven.Institute
Stating diaphragm material is polyethylene.Described electrolyte is the lithium hexafluoro phosphate (LiPF containing 1mol/L6) it is electrolyte, volume ratio carbon
Vinyl acetate (EC): diethyl carbonate (DEC): Ethyl methyl carbonate (EMC)=1:1:1 is the electrolyte of solvent.
Embodiment 1
The method preparing porous carbon materials for template with metal organic frame is described in detail by the present embodiment.
A kind of method preparing porous carbon materials for template with metal organic frame, comprises the steps:
(1) synthesis 5-(4-pyridin-4-yl-benzamido)-M-phthalic acid (H2PYBI)
Referring to Fig. 1, it is the synthetic reaction step schematic diagram of the organic ligand in the present invention.Weigh 35.144mmol respectively
The sodium carbonate of 4-bromopyridine hydrochloride, the 4-Carboxybenzeneboronic acid of 35.144mmol and 10mmol join in toluene solution,
Adding the four triphenyl phosphorus palladiums of 0.08mmol, under catalyst four triphenyl phosphorus palladium effect, reaction 10h obtains white intermediate product.
Intermediate product is dried, adds thionyl chloride, reflux under 80 °, be evaporated excess of solvent after having reacted, obtain yellow solid.
Yellow solid is mixed with 5-amino isophthalic acid in DMF, reacts 3h under room temperature, reactant liquor is joined 500mL
Distilled water in, separate out a large amount of solid, be H2PYBI part.
(2) synthesis Zn-MOF material
Weigh the Zn (NO of 0.1mmol3)2·6H2The H of O and 0.05mmol2It is 1:1's that PYBI is dissolved in the volume ratio of 6mL
DMF and H2After in O mixed solvent, in the reactor that liner is politef material, after 80 ° of reacting by heating 24h,
It is down to room temperature, obtains Zn-MOF material.
(3) using the Zn-MOF material that obtains in step (2) as presoma, in a nitrogen atmosphere, 6h are calcined in 900 °
Obtain porous carbon materials.
The present embodiment additionally provides a kind of method using described porous carbon materials to prepare lithium ion battery.Concrete, by porous carbon
Material, Kynoar, conductive acetylene white carbon black 8:1:1 in mass ratio mix, and are solvent furnishing pulpous state with N-Methyl pyrrolidone,
It is coated on Copper Foil, in the baking oven of 80 °, is first dried 1h, then in 120 ° of dry 10h in vacuum drying oven.Cut into slices after roll-in,
Obtain circular electric pole piece.By electrode slice, polyethylene diagrams material, electrolyte is the LiPF of 1mol/L6, solvent be that volume ratio is
The electrolyte of the mixed solution of EC, DEC and EMC of 1:1:1 is assembled into lithium ion battery.The most described lithium from
Sub-battery be model be the button cell of 2032, but be not limited to this.
Embodiment 2
In the present embodiment, a kind of method preparing porous carbon materials for template with metal organic frame, comprise the steps:
(1) synthesis 5-(4-pyridin-4-yl-benzamido)-M-phthalic acid (H2PYBI)
Referring to Fig. 1, it is the synthetic reaction step schematic diagram of the organic ligand in the present invention.Weigh 35.144mmol respectively
The sodium carbonate of 4-bromopyridine hydrochloride, the 4-Carboxybenzeneboronic acid of 35.144mmol and 10.5mmol join in toluene solution,
Adding the four triphenyl phosphorus palladiums of 0.08mmol, under catalyst four triphenyl phosphorus palladium effect, reaction 14h obtains white intermediate product.
Intermediate product is dried, adds thionyl chloride, reflux under 80 °, be evaporated excess of solvent after having reacted, obtain yellow solid.
Yellow solid is mixed with 5-amino isophthalic acid in DMF, reacts 1h under room temperature, reactant liquor is joined 500mL
Distilled water in, separate out a large amount of solid, be H2PYBI organic ligand.
(2) synthesis Zn-MOF material
Weigh the Zn (NO of 0.3mmol3)2·6H2The H of O and 0.2mmol2It is 1:1's that PYBI is dissolved in the volume ratio of 6mL
DMF and H2After in O mixed solvent, in the reactor that liner is politef material, after 40 ° of reacting by heating 28h,
It is down to room temperature, obtains Zn-MOF material.
(3) using the Zn-MOF material that obtains in step (2) as presoma, in a nitrogen atmosphere, 8h are calcined in 900 °
Obtain porous carbon materials.
The present embodiment additionally provides a kind of method using described porous carbon materials to prepare lithium ion battery.Concrete, by porous carbon
Material, Kynoar, conductive acetylene white carbon black 8:1:1 in mass ratio mix, and are solvent furnishing pulpous state with N-Methyl pyrrolidone,
It is coated on Copper Foil, in the baking oven of 60 °, is first dried 3h, then in 110 ° of dry 12h in vacuum drying oven.Cut into slices after roll-in,
Obtain circular electric pole piece.By electrode slice, polyethylene diagrams material, electrolyte is the LiPF of 1mol/L6, solvent be that volume ratio is
The electrolyte of the mixed solution of EC, DEC and EMC of 1:1:1 is assembled into lithium ion battery.The most described lithium from
Sub-battery be model be the button cell of 2032, but be not limited to this.
Embodiment 3
In the present embodiment, a kind of method preparing porous carbon materials for template with metal organic frame, comprise the steps:
(1) synthesis 5-(4-pyridin-4-yl-benzamido)-M-phthalic acid (H2PYBI)
Referring to Fig. 1, it is the synthetic reaction step schematic diagram of the organic ligand in the present invention.Weigh 35.144mmol respectively
The sodium carbonate of 4-bromopyridine hydrochloride, the 4-Carboxybenzeneboronic acid of 35.144mmol and 15mmol join in toluene solution,
Adding the four triphenyl phosphorus palladiums of 0.08mmol, under catalyst four triphenyl phosphorus palladium effect, reaction 6h obtains white intermediate product.
Intermediate product is dried, adds thionyl chloride, reflux under 80 °, be evaporated excess of solvent after having reacted, obtain yellow solid.
Yellow solid is mixed with 5-amino isophthalic acid in DMF, reacts 6h under room temperature, reactant liquor is joined 500mL
Distilled water in, separate out a large amount of solid, be H2PYBI organic ligand.
(2) synthesis Zn-MOF material
Weigh the Zn (NO of 0.1mmol3)2·6H2The H of O and 0.2mmol2It is 1:1's that PYBI is dissolved in the volume ratio of 6mL
DMF and H2After in O mixed solvent, in the reactor that liner is politef material, after 60 ° of reacting by heating 20h,
It is down to room temperature, obtains Zn-MOF material.
(3) using the Zn-MOF material that obtains in step (2) as presoma, in a nitrogen atmosphere, 7h are calcined in 900 °
Obtain porous carbon materials.
The present embodiment additionally provides a kind of method using described porous carbon materials to prepare lithium ion battery.Concrete, by porous carbon
Material, Kynoar, conductive acetylene white carbon black 8:1:1 in mass ratio mix, and are solvent furnishing pulpous state with N-Methyl pyrrolidone,
It is coated on Copper Foil, in the baking oven of 90 °, is first dried 0.5h, then in 130 ° of dry 8h in vacuum drying oven.Roll-in rear cutout
Sheet, obtains circular electric pole piece.By electrode slice, polyethylene diagrams material, electrolyte is the LiPF of 1mol/L6, solvent be volume
The electrolyte of the mixed solution than EC, DEC and EMC for 1:1:1 is assembled into lithium ion battery.Described in the present embodiment
Lithium ion battery be model be the button cell of 2032, but be not limited to this.
Effect example
Please refer to Fig. 2-4, its be respectively the present invention Zn-MOF material in the coordination environment figure of metallic zinc and porous carbon materials
The 3-D frame diagram of Zn-MOF.As can be known from Fig. 2, in Zn-MOF, metallic zinc uses 6 coordinations, is respectively from H2PYBI
The oxygen atom on carboxyl in part and the nitrogen-atoms on pyridine.Fig. 3 illustrates that Zn-MOF material exists the biggest hole, knot
Close Fig. 4 and show that described Zn-MOF material presents regularly arranged at three dimensions by the connection of paddle wheel formula.
Described Zn-MOF material is calcined under 900 ° of nitrogen atmospheres and obtains porous carbon materials.Referring to Fig. 5, it is the present invention
The PXRD figure of porous carbon materials in embodiment 1.It can be seen that two characteristic peaks of only material with carbon element, it was demonstrated that described material
It it is material with carbon element.
Referring to Fig. 6, it is the cycle performance test figure of the lithium ion battery using the porous carbon materials of the present invention to prepare.From figure
Knowable in, the lithium ion battery that described porous carbon materials is prepared as negative material, show good charge-discharge performance, first
Electric discharge can reach 2157mAh/g, and through the circulation of 100 discharge and recharges, its specific capacity can be stable at about 1104mAh/g,
Its coulombic efficiency is higher, shows good chemical property.
Referring to Fig. 7, it is the cyclic voltammetry figure of the lithium ion battery using the porous carbon materials of the present invention to prepare.In figure
It can be seen that there is the oxidoreduction peak of in the first run is tested, and this peak disappears in second and third is taken turns, and this is attributed to one
Individual irreversible process, i.e. forms SEI film at electrode surface.It is insoluble that SEI film has organic solvent, can be at organic electrolysis
Stable existence in liquid, such that it is able to the common embedding that effectively tissue solvent is follow-up, it is to avoid the solvent molecule damaging influence to electrode,
Thus improve the service life of battery.
Referring to Fig. 8, it is the constant current charge-discharge curve chart of the lithium ion battery using the porous carbon materials of the present invention to prepare.From
In figure understand, the charge and discharge platform of the lithium ion battery that described porous carbon materials prepares as negative material at below 1V,
There is the relatively low charge and discharge platform of ratio, illustrate that described porous carbon materials is well suited as the negative material of lithium ion battery.
Relative to prior art, the present invention uses nitrogen heterocyclic ring carboxylic acids part to synthesize Zn-MOF material, fully ensures that calcining
After the uniformity of lithium cell negative pole material nitrogen doped for preparing；While ensureing to improve negative material specific capacity, enter one
Step improves its cyclical stability.Described porous carbon materials is applied in lithium ion battery by the present invention as negative material, puts first
Electricity specific capacity is 2157mAh/g, and when charging and discharging currents density is 100mA/g, after circulating 100 times, specific capacity is stablized
1104mAh/g, has good cycle performance.Further, when porous carbon materials of the present invention is as negative material, negative pole
Material structure, specific surface area are adjustable, easily realize the raising of negative material chemical property；The knot of metal organic framework compound
Structure is adjustable with specific surface area, by selecting different calcining heats to realize the structure calcining the porous carbon materials prepared
Regulation and control, and then easily optimize the high performance lithium cell cathode material of acquisition.
The invention is not limited in above-mentioned embodiment, if to the various changes of the present invention or deformation without departing from the spirit of the present invention
And scope, if within the scope of these are changed and deform claim and the equivalent technologies belonging to the present invention, then the present invention is also intended to
Comprise these to change and deformation.
Claims (10)
1. method and the application preparing porous carbon materials with metal organic frame for template, it is characterised in that: comprise the following steps:
(1) synthesis organic ligand 5-(4-pyridin-4-yl-benzamido)-M-phthalic acid (H2PYBI)；
(2) synthesis Zn-MOF material: weigh Zn (NO3)2·6H2O and H2After PYBI is dissolved in solvent, in reactor
Reacting by heating, reaction is down to room temperature after terminating, is obtained Zn-MOF material；
(3) synthesizing porous material with carbon element: the Zn-MOF material obtained in step (2) is as presoma, at noble gas atmosphere
Enclose lower calcining and obtain porous carbon materials.
The method preparing porous carbon materials for template with metal organic frame the most according to claim 1, it is characterised in that: step
Suddenly in (2), Zn (NO3)2·6H2O and H2The mol ratio of PYBI is 2:1-1:2.
The method preparing porous carbon materials for template with metal organic frame the most according to claim 2, it is characterised in that: step
Suddenly in (2), Zn (NO3)2·6H2O and H2The mol ratio of PYBI is 2:1.
4. according to the method preparing porous carbon materials for template with metal organic frame described in any claim in claim 1-3,
It is characterized in that: in step (2), described solvent be volume ratio be DMF and the mixed solvent of water of 1:1.
The method preparing porous carbon materials for template with metal organic frame the most according to claim 1, it is characterised in that: step
Suddenly, in (1), weigh 4-bromopyridine hydrochloride, 4-Carboxybenzeneboronic acid and sodium carbonate and add in toluene, add four triphenyl phosphorus
Palladium makees catalyst, and reaction 6-14h obtains intermediate product；Dry intermediate product, after adding thionyl chloride back flow reaction, steam
Dry excess of solvent, obtains solid；Solid is mixed in DMF with 5-amino isophthalic acid, room temperature reaction 1-6h,
Reactant liquor is added to the distilled water of excess, separates out solid product, be H2PYBI organic ligand.
The method preparing porous carbon materials for template with metal organic frame the most according to claim 5, it is characterised in that: institute
State in step (1), the preferred 1:1:(0.28-0.43 of mol ratio of 4-bromopyridine hydrochloride, 4-Carboxybenzeneboronic acid and sodium carbonate),
Catalyst four triphenyl phosphorus palladium and the preferred 0.002:1 of mol ratio of 4-bromopyridine hydrochloride；In described step (1), add chlorine
Changing sulfoxide reflux temperature is 80 °.
The method preparing porous carbon materials for template with metal organic frame the most according to claim 4, it is characterised in that: institute
Stating heating-up temperature in step (2) and be 40-80 °, the response time is 20-28h.
8. according to preparing porous carbon materials with metal organic frame for template described in any claim in claim 1-3 or 5-7
Method, it is characterised in that: in described step (3), the Zn-MOF material obtained in step (2) as presoma,
Under nitrogen atmosphere, 6h is calcined in 900 °.
9. the preparation method of a lithium battery, it is characterised in that: comprise the following steps: by porous carbon materials, binding agent, conduction charcoal
Black it is mixed in proportion, with solvent furnishing pulpous state, is coated on Copper Foil, vacuum drying, cut into slices after roll-in, obtain circular electrode
Sheet；Electrode slice, diaphragm material, electrolyte are assembled into lithium ion battery；Described porous carbon materials is claim 1-8
The porous carbon materials that preparation method described in middle any claim prepares.
The preparation method of lithium battery the most according to claim 9, it is characterised in that: described binding agent is Kynoar, institute
Stating conductive black is conductive acetylene white carbon black, and described solvent is N-Methyl pyrrolidone；Described porous carbon materials, binding agent,
The mass ratio of conductive black is 8:1:1.
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