CN109727784A - Lithium titanate/carbon material compound, negative electrode material, negative electrode tab and hybrid super capacitor - Google Patents
Lithium titanate/carbon material compound, negative electrode material, negative electrode tab and hybrid super capacitor Download PDFInfo
- Publication number
- CN109727784A CN109727784A CN201711017872.9A CN201711017872A CN109727784A CN 109727784 A CN109727784 A CN 109727784A CN 201711017872 A CN201711017872 A CN 201711017872A CN 109727784 A CN109727784 A CN 109727784A
- Authority
- CN
- China
- Prior art keywords
- negative electrode
- lithium titanate
- carbon material
- compound
- weight
- 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.)
- Pending
Links
Classifications
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention belongs to new energy energy storage device fields, disclose compound, negative electrode material, negative electrode tab and the hybrid super capacitor of a kind of lithium titanate/carbon material, wherein, lithium titanate/carbon material compound contains lithium titanate and carbon material, wherein lithium titanate in-situ preparation, and on the basis of the total weight of the compound of the lithium titanate/carbon material, the content of the carbon material is 0.1-50 weight %, and the content of lithium titanate is 50-99.9 weight %.Hybrid super capacitor provided by the invention includes the negative electrode tab coated with negative electrode material, the negative electrode material contains the compound of the lithium titanate/carbon material, greatly improve the electric conductivity and energy storage characteristic of electrode, reduce the polarization phenomena of material internal, improve the cyclical stability and high rate performance of capacitor, it realizes the charge and discharge needs of big multiplying power, while improving the cycle life of capacitor.
Description
Technical field
The invention belongs to new energy energy storage device fields, and in particular to a kind of compound of lithium titanate/carbon material, cathode material
Material, negative electrode tab and hybrid super capacitor.
Background technique
If supercapacitor is divided above energy storage mechnism, supercapacitor is divided into double layer capacitor and pseudocapacitors.
It is a kind of novel energy storage apparatus, it has, and power density is high, the charging time is short, long service life, good temp characteristic, energy saving
And the features such as environmentally protective, the fields such as public transport, smart grid, portable digital product are had been widely used for, by more
Carry out more concerns.
However since there are the limitations in terms of energy density for double layer capacitor, supercapacitor is in high-power, high-energy
Development in terms of density encounters great challenge.In conjunction with double layer capacitor high power capacitive character feature and can quickly send out
The high energy battery material of raw redox reaction, preparing hybrid super capacitor becomes supercapacitor development of new generation
Important directions and trend.
Lithium titanate (Li4Ti5O12) there is high theoretical specific capacity (175mAh/g), excellent zero strain characteristic, good
The features such as electrochemical cycle stability become the important materials of high capacity supercapacitor of new generation, are worked by vast energy storage
The extensive concern of person.But Li4Ti5O12The intrinsic electronic conductivity of material is 10-9S/cm, electron conduction is poor, under high current
Polarization phenomena are serious, it is difficult to meet requirement of the supercapacitor for high power, long-life, for Li4Ti5O12It is modified into
For the Main way studied at present.
Summary of the invention
The purpose of the invention is to overcome the power density of hybrid super capacitor of the existing technology low and capacity
Low problem provides compound, negative electrode material, negative electrode tab and the hybrid super capacitor of a kind of lithium titanate/carbon material, the mixing
Supercapacitor greatly improves the electric conductivity and energy storage characteristic of electrode, reduces the polarization phenomena of material internal, improves electricity
The cyclical stability and high rate performance of container, realize the charge and discharge needs of big multiplying power, while improving the cycle life of capacitor.
To achieve the goals above, one aspect of the present invention provides a kind of compound of lithium titanate/carbon material, wherein should
Compound contains lithium titanate and carbon material, wherein lithium titanate in-situ preparation, and with the total of the compound of the lithium titanate/carbon material
On the basis of weight, the content of the carbon material is 0.1-50 weight %, and the content of the lithium titanate is 50-99.9 weight %.
Preferably, the carbon material is carbon nanotube and/or graphene oxide.
Another aspect of the present invention additionally provides a kind of preparation method of the compound of lithium titanate/carbon material, wherein this method
The following steps are included:
(1) it is molten that butyl titanate is added drop-wise to preparation A in the dispersion liquid of the alcohol containing carbon nanotube and/or graphene oxide
Liquid；And by lithium acetate and deionized water and/or ethyl alcohol mixed preparing B solution；
(2) B solution is added drop-wise in solution A and carries out solvent thermal reaction；
(3) reactant after solvent thermal reaction is subjected to high-temperature heat treatment.
Preferably, in step (1), on the basis of the total volume of the alcohol of 100mL, the carbon nanotube and/or oxidation stone
The dosage of black alkene is 0.01-6g, and the dosage of the butyl titanate is 0.01-20.4g；With the mixed solution of the alcohol of 100mL
On the basis of total volume, the dosage of the lithium acetate is 0.01-3.35g.
It preferably, further include carrying out the reactant after solvent thermal reaction at drying before carrying out high-temperature heat treatment
Reason, and
The condition of solvent thermal reaction: temperature is 120-180 DEG C, and the time is 10-25 hours；
The condition of high-temperature heat treatment: temperature is 700-900 DEG C, and the time is 3-5 hours.
Another aspect of the present invention additionally provides a kind of negative electrode material, wherein it is multiple that the negative electrode material contains lithium titanate/carbon material
Close object, conductive agent A and binder A, wherein the lithium titanate/carbon material compound is that lithium titanate/carbon material described above is multiple
Close lithium titanate/carbon material compound of the preparation of method described in object or above-mentioned any one.
Preferably, on the basis of the total weight of the negative electrode material, the content of the conductive agent A is 5-20 weight %, institute
The content for stating binder A is 3-10 weight %, and the content of the compound of the lithium titanate/carbon material is 70-92 weight %.
Another aspect of the present invention additionally provides a kind of negative electrode tab, wherein the negative electrode tab include cathode core and its extremely
The negative electrode material described above of the part coating of a few side surface.
Preferably, the negative electrode tab with a thickness of 35-60 μm and the part of a side surface of the cathode core coating
Negative electrode material applied thickness be 15-40 μm.
Another aspect of the present invention additionally provides a kind of hybrid super capacitor, the hybrid super capacitor include positive plate,
Negative electrode tab, diaphragm and electrolyte, wherein the negative electrode tab is negative electrode tab described above.
Preferably, the positive plate includes the positive electrode of positive core and the part coating of its at least side surface,
The positive electrode contains conductive agent B, binder B and electric double layer energy storage material and the electric double layer energy storage material for activity
One of charcoal, graphene, carbon nanotube and carbon aerogels are a variety of.
Preferably, on the basis of the total weight of the positive electrode, the content of the conductive agent B is 5-20 weight %, institute
The content for stating binder B is 3-10 weight %, and the content of the electric double layer energy storage material is 70-92 weight %.
Preferably, the positive plate with a thickness of 40-70 μm and the part coating of a side surface of the positive core
Positive electrode applied thickness be 20-50 μm.
Preferably, the diaphragm is one of polyethene microporous membrane, microporous polypropylene membrane, inorganic ceramic membrane and paper diaphragm
Or it is a variety of.
Preferably, the solvent in the electrolyte is acetonitrile, and solute is lithium hexafluoro phosphate, and the concentration of the solute is
The ionic conductivity of 0.8-1.2mol/L and the electrolyte is 50-60mS/cm.
Through the above technical solutions, hybrid super capacitor provided by the invention, is with lithium titanate/carbon material compound
Negative electrode material is coated on at least part of a side surface of cathode core, and the carbon material is carbon nanotube and/or oxidation
Graphene substantially increases the electric conductivity and energy storage characteristic of electrode, reduces the polarization phenomena of material internal, improve capacitor
Cyclical stability and high rate performance, realize the charge and discharge needs of big multiplying power, while improving the cycle life of capacitor.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the SEM photograph of the lithium titanate/carbon material compound prepared by embodiment 1；
Fig. 2 is the TEM photo of the lithium titanate/carbon material compound prepared by embodiment 1；
Fig. 3 is the curve graph of the cycle performance of the hybrid super capacitor prepared by embodiment 1.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of compound of lithium titanate/carbon material, wherein the compound contain lithium titanate and
Carbon material, wherein lithium titanate in-situ preparation, and on the basis of the total weight of the compound of the lithium titanate/carbon material, the carbon
The content of material can be 0.1-50 weight %, and the content of the lithium titanate is 50-99.9 weight %；Preferably, with the titanium
On the basis of the total weight of the compound of sour lithium/carbon material, the content of the carbon material is 0.1-10 weight %, the lithium titanate
Content is 90.0-99.9 weight %；In the present invention, the content of carbon material is controlled in above range, leading for material can be improved
Electrically, and the capacity of cathode can be maintained.
According to the present invention, the carbon nanotube refers to the seamless nanotube as made of single layer or the curling of Multi-layer graphite piece.
The carbon nanotube can be one of single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube or a variety of；It is preferred that
Ground, the carbon nanotube can be single-walled carbon nanotube or multi-walled carbon nanotube；It is highly preferred that the carbon nanotube is multi wall carbon
Nanotube.The carbon nanotube internal diameter ID can be 2-20nm, and outer diameter OD≤30nm, length of carbon nanotube can be 5-30 μm,
Preferably, the carbon nanotube internal diameter ID is 5-15nm, and outer diameter OD≤30nm, length of carbon nanotube is 10-30 μm.
According to the present invention, the graphene oxide (Graphite Oxide) can be lamella solid either dispersion liquid.
Another aspect of the present invention additionally provides a kind of preparation method of the compound of lithium titanate/carbon material, wherein this method
The following steps are included:
(1) it is molten that butyl titanate is added drop-wise to preparation A in the dispersion liquid of the alcohol containing carbon nanotube and/or graphene oxide
Liquid；And by lithium acetate and deionized water and/or ethyl alcohol mixed preparing B solution；
(2) B solution is added drop-wise in solution A and carries out solvent thermal reaction；
(3) reactant after solvent thermal reaction is subjected to high-temperature heat treatment.
According to the present invention, in step (1), when preparing solution A, on the basis of the total volume of the alcohol of 100mL, the carbon
The dosage of nanotube and/or graphene oxide can be 0.05-6g, preferably 0.06-1.2g, more preferably 0.08-0.3g, institute
The dosage for stating butyl titanate (TBOT) can be 0.01-50g, preferably 5-30g, more preferably 6-11g.
According to the present invention, in step (1), when preparing B solution, the total volume with the mixed solution of the alcohol of 100mL is
Benchmark, the dosage of the lithium acetate can be 0.01-20g, preferably 1-10g, more preferably 1.5-5g；In the present invention, when
When using the total volume of the deionized water of 100mL and the mixed solution of alcohol as benchmark, the dosage of the deionized water and the alcohol
Than being preferably 1:10-50.
According to the present invention, in step (1), carbon nanotube and/or graphene oxide is distributed in alcoholic solvent and are formulated as
The dispersion liquid of alcohol containing carbon nanotube and/or graphene oxide, wherein the alcohol is not particularly limited, and can be anhydrous
One of ethyl alcohol, propyl alcohol and butanol are a variety of, in the present invention, it is preferred to be dehydrated alcohol；And by carbon nanotube and/or
Graphene oxide, which is distributed in alcoholic solvent, preferably to carry out under conditions of ultrasound, and the condition and equipment of the ultrasound be not specific
It limits, can be the conventional selection of this field；And it is added drop-wise to by butyl titanate containing carbon nanotube and/or graphite oxide
When in the dispersion liquid of the alcohol of alkene, which is not particularly limited, for example, can be dripped with the drop rate of 0.01-0.5mL/s
Add；And butyl titanate is added drop-wise in the dispersion liquid of the alcohol containing carbon nanotube and/or graphene oxide and is preferably being stirred
Under conditions of carry out, and stirring condition and equipment be not particularly limited, can be this field conventional selection.
According to the present invention, in step (2), B solution is added drop-wise to the drop rate in solution A and is not particularly limited, example
Such as, it can be added dropwise with the drop rate of 0.01-0.5mL/s；And it is added drop-wise in solution A preferably by B solution in the item of stirring
It is carried out under part, wherein the equipment of stirring can be magnetic stirring apparatus, and the rate of stirring can be 10-100r/min.
According to the present invention, in step (2), solvent thermal reaction 10- can be carried out under conditions of temperature is 120-180 DEG C
25 hours, it is preferable that carried out solvent thermal reaction 23.5-24.5 hours under conditions of temperature is 125-150 DEG C.
According to the present invention, in step (3), before carrying out high-temperature heat treatment, further including will be after solvent thermal reaction
Reactant carries out drying and processing, such as the reactant after solvent thermal reaction can be put into glass culture dish, is in temperature
It is dried 11-13 hours under conditions of 50-70 DEG C, it is preferable that dried 11.5-12.5 hours under conditions of temperature is 55-65 DEG C；
And the drying equipment is not particularly limited, such as can be baking oven.
According to the present invention, in step (3), powder dry after drying is placed in quartz boat, it can be in tube furnace
Middle carry out high-temperature heat treatment, wherein can temperature be 700-900 DEG C under conditions of carry out high-temperature heat treatment 3-5 hours, preferably
Ground carries out high-temperature heat treatment 3.5-4.5 hours, wherein the heating rate of tube furnace does not have under conditions of temperature is 750-850 DEG C
There is specific restriction, in the present invention, heating rate is preferably 4-5 DEG C/min, more preferably 5 DEG C/min；And in tube furnace
Calcining preferably carry out under the protective atmosphere of high pure nitrogen when high-temperature heat treatment.
Another aspect of the present invention additionally provides a kind of negative electrode material, wherein it is multiple that the negative electrode material contains lithium titanate/carbon material
Close object, conductive agent A and binder A, wherein the lithium titanate/carbon material compound is that lithium titanate/carbon material described above is multiple
Close lithium titanate/carbon material compound of the preparation of method described in object or above-mentioned any one.
According to the present invention, on the basis of the total weight of the negative electrode material, the content of the conductive agent A is 5-20 weight
% is measured, the content of the binder A is 3-10 weight %, and the content of the compound of the lithium titanate/carbon material is 70-92 weight
Measure %；
Preferably, on the basis of the total weight of the negative electrode material, the content of the conductive agent A is 5-20 weight %, institute
The content for stating binder A is 3-10 weight %, and the content of the compound of the lithium titanate/carbon material is 70-92 weight %；
Another aspect of the present invention additionally provides a kind of negative electrode tab, wherein the negative electrode tab include cathode core and its extremely
The negative electrode material described above of the part coating of a few side surface.
According to the present invention, the thickness of the negative electrode tab can be a side surface of 35-60 μm and the cathode core
The applied thickness of the negative electrode material of part coating can be 15-40 μm；Preferably, the negative electrode tab with a thickness of 35-50 μm, with
And the applied thickness of the negative electrode material of the part coating of a side surface of the cathode core is 15-30 μm.In the present invention, such as
If the applied thickness of the negative electrode material of the part coating of one side surface of fruit cathode core is too thick, the capacity of cathode will be excessive
Can not really use, thus the applied thickness for the negative electrode material that the part of a side surface of cathode core is applied and
The thickness control of negative electrode tab is preferable within this range.
According to the present invention, since the thickness of positive and negative anodes has the relationship of a capacity matching, the specific capacity of cathode is much larger than just
Pole material, therefore, in the present invention, it is preferred to, the capacity ratio of the anode and cathode is relatively good between 1:2-4.
Another aspect of the present invention additionally provides a kind of hybrid super capacitor, the hybrid super capacitor include positive plate,
Negative electrode tab, diaphragm and electrolyte, wherein the negative electrode tab is negative electrode tab described above.
According to the present invention, the positive plate includes the positive material of positive core and the part coating of its at least side surface
Material, the positive electrode contains conductive agent B, binder B and electric double layer energy storage material and the electric double layer energy storage material can be with
For one of active carbon, graphene, carbon nanotube and carbon aerogels or a variety of, wherein the carbon nanotube can be single wall
One of carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube are a variety of；The graphene is using physics stripping method
The single-layer graphene and/or multi-layer graphene of preparation, the number of plies of the multi-layer graphene are 1-10 layers；Preferably, double electricity
Layer energy storage material is active carbon, also, the partial size of the active carbon is 10-100 μm, specific surface area 500-2000m2/g。
According to the present invention, on the basis of the total weight of the positive electrode, the content of the conductive agent B can be 5-20 weight
% is measured, the content of the binder B can be 3-10 weight %, and the content of the electric double layer energy storage material can be 70-92 weight
Measure %.
Preferably, on the basis of the total weight of the positive electrode, the content of the conductive agent B is 5-20 weight %, institute
The content for stating binder B is 3-10 weight %, and the content of the electric double layer energy storage material is 70-92 weight %.
According to the present invention, the thickness of the positive plate can be a side surface of 40-70 μm and the positive core
The applied thickness of the positive electrode of part coating can be 20-50 μm；Preferably, the positive plate with a thickness of 40-60 μm, with
And the applied thickness of the positive electrode of the part coating of a side surface of the positive core is 20-40 μm.In the present invention, such as
Fruit positive plate thickness is too thick, then the cyclical stability for being easy to peel off to influence capacitor as the positive electrode matter of active matter；
If positive plate thickness is too thin, negative electrode material can not give full play to the theoretical capacity of itself, which exists
Capacity decline in unit volume, and within the above range by the thickness control of positive plate and positive electrode, hybrid super electricity
The performance and stability of container can achieve most preferably.
According to the present invention, the conductive agent A and conductive agent B is not particularly limited, and can be the normal of those skilled in the art
Rule selection, for example, the conductive agent A and conductive agent B can be respectively conductive black, carbon nanotube, carbon nano-fiber, single layer stone
One of black alkene is a variety of；Preferably, the conductive agent A and conductive agent are respectively conductive black.
According to the present invention, described binder A and binder B is not particularly limited, and can be the normal of those skilled in the art
Rule selection, for example, the binder A and binder B can be respectively polytetrafluoroethylene (PTFE), butadiene-styrene rubber, acrylic resin, gather partially
One of vinyl fluoride is a variety of；Preferably, the binder A and binder B are respectively Kynoar.
According to the present invention, the diaphragm can be polyethene microporous membrane, microporous polypropylene membrane, inorganic ceramic membrane and cellulose
One of paper diaphragm is a variety of；Preferably, the diaphragm is cellulose paper diaphragm.
According to the present invention, the solvent in the electrolyte can be acetonitrile, and solute can be lithium hexafluoro phosphate, and described molten
The concentration of matter can be that the ionic conductivity of 0.8-1.2mol/L and the electrolyte can be 50-60mS/cm.
According to the present invention, the preparation of the positive plate is not particularly limited, for example, can using electric double layer energy storage material as
Then active material mixes in proportion with conductive agent B, binder B, solvent is added and is modulated into slurry, is coated in using coating machine
In current collector aluminum foil, drying is rolled, is punched, being dried in vacuo and be prepared into positive plate；And active material, conductive agent B, bonding
The mass ratio of the dosage of agent B can be 6-8:1-3:1.
According to the present invention, the preparation of the negative electrode tab is not particularly limited, for example, lithium titanate/carbon material can be answered
Object is closed as active material, is then mixed in proportion with conductive agent A, binder A, solvent is added and is modulated into slurry, using coating
Coated in current collector aluminum foil, drying is rolled, is punched, being dried in vacuo and be prepared into negative electrode tab machine；Wherein, in the present invention, institute
Lithium titanate/carbon material compound is stated using above-mentioned preparation method to prepare；And active material, conductive agent A, binder A
The mass ratio of dosage can be 6-8:1-3:1.
According to the present invention, the preparation of the hybrid super capacitor is not particularly limited, for example, by positive plate, diaphragm, electricity
Solution liquid, negative electrode tab, steel disc, spring leaf are sequentially placed in the shell of CR2032, are assembled into button hybrid capacitor by encapsulation
Device.In the present invention, the portion of at least side surface using lithium titanate/carbon material compound as negative electrode material coated in cathode core
On point, and the carbon material is carbon nanotube and/or graphene oxide, and electric conductivity and the energy storage for substantially increasing electrode are special
Property, the polarization phenomena of material internal are reduced, the cyclical stability and high rate performance of capacitor are improved, realize the charge and discharge of big multiplying power
It needs, while improving the cycle life of capacitor.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example, unless otherwise instructed, each material and reagent can be commercially available.
Carbon nanotube is purchased from South Korea Jin Hu company, and graphene oxide is purchased from the limited public affairs of the big charcoal element new material science and technology share in side
Department, carbon black are purchased from Taiyuan Li Yuanli electricity Science and Technology Ltd., and active carbon is purchased from Kuraray Co., Ltd.；
The scanning electron microscope of SEM for test sample is purchased from high and new technology company, Hitachi；
The transmission scanning electron microscope of TEM for test sample is purchased from high and new technology company, Hitachi；
The blue electrical testing instrument of cycle performance for test sample wins the limited public affairs of battery testing instrument purchased from Wuhan indigo plant
Department.
The test method of the capacity of the button hybrid super capacitor are as follows:
The above-mentioned button-shaped supercapacitor prepared is tested using blue electric battery test apparatus, setting constant current is filled
Discharge cycles process, maintenance current density are 500mAg-1Charge and discharge cycles test is carried out, using all electrode materials of positive and negative anodes
Quality calculates power density as gross mass.
Embodiment 1
The present embodiment is used to illustrate the preparation method and hybrid super electricity of lithium titanate/carbon material compound of the invention
Container.
(1) preparation of lithium titanate/carbon material compound:
Firstly, 0.3g purifying carbon nano-tube is distributed in 100mL dehydrated alcohol, ultrasonic disperse 60min, be formulated as containing
The dispersion liquid of the alcohol of carbon nanotube, then, by 10.2g butyl titanate (TBOT) with the dropwise addition of 0.01mL/s under magnetic stirring
Rate is added drop-wise in above-mentioned suspension dropwise and is configured to solution A；1.6632g lithium acetate is dissolved into 2mL deionized water and 23mL
B solution is configured in the mixed solution of dehydrated alcohol；
Secondly, B solution is dripped dropwise with the drop rate of 0.01mL/s in the case where strong magnetic stirring rate is 80r/min
It is added in solution A, continues stirring at room temperature for 24 hours, then seal 150 DEG C of solvent thermal reactions for 24 hours；Mixed liquor is put into glass training later
It supports in ware, keeps 60 DEG C of dry 12h in an oven；
Then, dried powder is put into quartz boat, makees high-temperature heat treatment in tube furnace, with high pure nitrogen
Make protective atmosphere, 800 DEG C of heat preservation 4h (heating rate is 5 DEG C/min), obtaining target product is that lithium titanate/carbon material is compound
Object (Li4Ti5O12/ CNTs composite material)；Wherein, described on the basis of the total weight of the compound of the lithium titanate/carbon material
The content of carbon material is 12% (weight).
If Fig. 1 is the Li prepared by embodiment 14Ti5O12The SEM photograph of/CNTs, Fig. 2 are the metatitanic acids prepared by embodiment 1
The TEM photo of lithium/carbon material compound, as can be seen that Li from Fig. 1 and Fig. 24Ti5O12Nano particle is uniformly attached to carbon
On nanotube.
(2) preparation of negative electrode material
By the Li of above-mentioned synthesis4Ti5O12(specific binder is poly- by/CNTs composite material, conductive black and binder A
Vinylidene) weighed according to the mass ratio of 7:2:1 after be uniformly mixed, be then added solvent be placed in magnetic stirring apparatus stir it is mixed
Conjunction is modulated into negative electrode material.
(3) preparation of negative electrode tab
Negative electrode material is applied in the part of a current collector aluminum foil at least side surface, drying is rolled, is punched, being dried in vacuo
It is prepared into negative electrode tab；Wherein, the negative electrode tab with a thickness of 35 μm and the part of a side surface of the cathode core coating
Negative electrode material applied thickness be 15 μm.
(4) preparation of positive plate
The production of positive plate: by electric double layer energy storage material active carbon (specific surface area 1600m2/ g) as active material,
Conductive black, binder B (PVDF) are uniformly mixed after weighing according to the mass ratio of 7:2:1, and solvent is then added and is placed on magnetic force
It is stirred in blender and is modulated into slurry, be then coated on a current collector, drying is rolled, is punched, being dried in vacuo system
For at positive plate；Wherein, the positive plate with a thickness of 50 μm and the part coating of a side surface of the positive core
The applied thickness of positive electrode is 25 μm.
(5) preparation of mixed capacitor
Positive plate, diaphragm, electrolyte, negative electrode tab, steel disc, spring leaf are sequentially placed in the shell of CR2032, by envelope
Dress is assembled into button hybrid super capacitor.Wherein, the solvent in the electrolyte is acetonitrile, and solute is lithium hexafluoro phosphate, and
The concentration of the solute can be that the ionic conductivity of 0.8mol/L and the electrolyte can be 50mS/cm.
The power density of the hybrid super capacitor prepared by embodiment 1 is 26.5Wh/kg.
Fig. 3 is the curve graph of the cycle performance of the hybrid super capacitor that is prepared by embodiment 1 when electric current is 5mA, from
The value of the trend and coulombic efficiency (referring to discharge capacity of the cell and with the ratio between charging capacity in cyclic process) of curve is it is found that this is mixed
Closing supercapacitor has good cyclical stability and high coulombic efficiency；And the hybrid super electricity prepared by embodiment 1
Container substantially increases the electric conductivity and energy storage characteristic of electrode, reduces the polarization phenomena of material internal, improves following for capacitor
Ring stability and high rate performance, realize the charge and discharge needs of big multiplying power, while improving the cycle life of capacitor.
Embodiment 2
The present embodiment is used to illustrate the preparation method and hybrid super electricity of lithium titanate/carbon material compound of the invention
Container.
(1) preparation of lithium titanate/carbon material compound:
Firstly, 0.240g graphene oxide (GO) is distributed in 300mL dehydrated alcohol, ultrasonic disperse 60min is formulated as
The dispersion liquid of alcohol containing graphene oxide, then, by 17.782g butyl titanate (TBOT) with 0.5mL/ under magnetic stirring
The drop rate of s is added drop-wise in above-mentioned suspension dropwise and is configured to solution A；4.793g lithium acetate is dissolved into 50mL dehydrated alcohol
In be configured to B solution；
Secondly, B solution is added dropwise dropwise with the drop rate of 0.5mL/s in the case where strong magnetic stirring rate is 80r/min
Into solution A, continue stirring at room temperature for 24 hours, then seal 150 DEG C of solvent thermal reactions for 24 hours；Mixed liquor is put into glass culture later
In ware, 60 DEG C of dry 12h are kept in an oven；
Then, dried powder is put into quartz boat, makees high-temperature heat treatment in tube furnace, with high pure nitrogen
Make protective atmosphere, 800 DEG C of heat preservation 4h (heating rate is 5 DEG C/min), obtaining target product is that lithium titanate/carbon material is compound
Object (Li4Ti5O12/ RGO composite material, wherein RGO is obtained from being reduced after GO is heat-treated, that is, reduction-oxidation graphite
Alkene), wherein on the basis of the total weight of the compound of the lithium titanate/carbon material, the content of the carbon material is 5 weight %.
(2) preparation of negative electrode material
By the Li of above-mentioned synthesis4Ti5O12/ RGO composite material, conductive black and binder A (PVDF) according to 7:2:1 matter
For amount than being uniformly mixed after weighing, then addition solvent, which is placed on to be stirred in magnetic stirring apparatus, is modulated into negative electrode material.
(3) preparation of negative electrode tab
Negative electrode material is applied in the part of a current collector aluminum foil at least side surface, drying is rolled, is punched, being dried in vacuo
It is prepared into negative electrode tab；Wherein, the negative electrode tab with a thickness of 35 μm and the part of a side surface of the cathode core coating
Negative electrode material applied thickness be 15 μm.
(4) preparation of positive plate
The production of positive plate: by electric double layer energy storage material active carbon (specific surface area 1600m2/ g) as active material,
Conductive black, binder B (PVDF) are uniformly mixed after weighing according to the mass ratio of 7:2:1, and solvent is then added and is placed on magnetic force
It is stirred in blender and is modulated into slurry, be then coated on a current collector, drying is rolled, is punched, being dried in vacuo system
For at positive plate；Wherein, the positive plate with a thickness of 50 μm and the part coating of a side surface of the positive core
The applied thickness of positive electrode is 25 μm.
(5) preparation of mixed capacitor
Positive plate, diaphragm, electrolyte, negative electrode tab, steel disc, spring leaf are sequentially placed in the shell of CR2032, by envelope
Dress is assembled into button hybrid super capacitor.Wherein, the solvent in the electrolyte is acetonitrile, and solute is lithium hexafluoro phosphate, and
The concentration of the solute can be that the ionic conductivity of 1.2mol/L and the electrolyte can be 60mS/cm.
The power density of the hybrid super capacitor prepared by embodiment 2 is 24.6Wh/kg.
The electric conductivity and energy storage characteristic of electrode are substantially increased by hybrid super capacitor prepared by embodiment 2, are reduced
The polarization phenomena of material internal improve the cyclical stability and high rate performance of capacitor, realize the charge and discharge needs of big multiplying power, together
The cycle life of Shi Tigao capacitor.
Comparative example 1
Prepare hybrid super capacitor according to the method for embodiment 1, institute the difference is that, do not carry out step (1) conjunction
At lithium titanate/carbon material compound (Li4Ti5O12/ CNTs composite material), thus in step (2), by Li4Ti5O12/CNTs
Composite material replaces with lithium titanate, and the power density of the hybrid super capacitor as a result prepared is 20.1Wh/kg.
Comparative example 2
Prepare hybrid super capacitor according to the method for embodiment 1, institute the difference is that, in step (1), 120
DEG C solvent thermal reaction 30h is carried out, the power density of the hybrid super capacitor as a result prepared is 15.3Wh/kg.
Comparative example 3
Prepare hybrid super capacitor according to the method for embodiment 1, institute the difference is that, in step (1), 120
DEG C solvent thermal reaction 8h is carried out, the power density of the hybrid super capacitor as a result prepared is 17Wh/kg.
Comparative example 4
Prepare hybrid super capacitor according to the method for embodiment 1, institute the difference is that, carbon nanotube, four fourth of metatitanic acid
Ester, lithium acetate dosage not within limited range of the present invention, specifically, the dosage of the carbon nanotube is 7g, institute
The dosage for stating butyl titanate is 21g；On the basis of the total volume of the mixed solution of the alcohol of 100mL, the dosage of the lithium acetate
For 3.5g, the power density of the hybrid super capacitor as a result prepared is 18.9Wh/kg.
By the result of embodiment 1-2 and comparative example 1-4: hybrid super capacitor provided by the invention, with metatitanic acid
Lithium/carbon material compound is coated on at least part of a side surface of cathode core for negative electrode material, and the carbon material
For carbon nanotube and/or graphene oxide, the electric conductivity and energy storage characteristic of electrode are substantially increased, the pole of material internal is reduced
Change phenomenon, improves the cyclical stability and high rate performance of capacitor, realize the charge and discharge needs of big multiplying power, while improving capacitor
Cycle life.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (15)
1. a kind of compound of lithium titanate/carbon material, which is characterized in that the compound contains lithium titanate and carbon material, wherein titanium
Sour lithium in-situ preparation, and on the basis of the total weight of the compound of the lithium titanate/carbon material, the content of the carbon material is
0.1-50 weight %, the content of the lithium titanate are 50-99.9 weight %.
2. compound according to claim 1, wherein the carbon material is carbon nanotube and/or graphene oxide.
3. the preparation method of lithium titanate/carbon material compound of any of claims 1 or 2, which is characterized in that this method include with
Lower step:
(1) butyl titanate is added drop-wise in the dispersion liquid of the alcohol containing carbon nanotube and/or graphene oxide and prepares solution A；
And by lithium acetate and deionized water and/or ethyl alcohol mixed preparing B solution；
(2) B solution is added drop-wise in solution A and carries out solvent thermal reaction；
(3) reactant after solvent thermal reaction is subjected to high-temperature heat treatment.
4. preparation method according to claim 3, wherein in step (1), on the basis of the total volume of the alcohol of 100mL,
The carbon nanotube and/or the dosage of graphene oxide are 0.01-6g, and the dosage of the butyl titanate is 0.01-20.4g；
On the basis of the total volume of the mixed solution of the alcohol of 100mL, the dosage of the lithium acetate is 0.01-3.35g.
5. preparation method according to claim 3, wherein further including before carrying out high-temperature heat treatment will be anti-through solvent heat
Reactant after answering carries out drying and processing, and
The condition of solvent thermal reaction: temperature is 120-180 DEG C, and the time is 15-25 hours；
The condition of high-temperature heat treatment: temperature is 700-900 DEG C, and the time is 3-5 hours.
6. a kind of negative electrode material, which is characterized in that the negative electrode material contains lithium titanate/carbon material compound, conductive agent A and bonding
Agent A, wherein the lithium titanate/carbon material compound is lithium titanate/carbon material compound of any of claims 1 or 2 or power
Lithium titanate/carbon material compound that benefit requires method described in any one of 3-5 to prepare.
7. negative electrode material according to claim 6, wherein on the basis of the total weight of the negative electrode material, the conduction
The content of agent A is 5-20 weight %, and the content of the binder A is 3-10 weight %, the compound of the lithium titanate/carbon material
Content be 70-92 weight %.
8. a kind of negative electrode tab, which is characterized in that the negative electrode tab includes cathode core and the part painting of its at least side surface
Negative electrode material described in deposited claim 6 or 7.
9. negative electrode tab according to claim 8, wherein the negative electrode tab with a thickness of 35-60 μm and the cathode core
The applied thickness of the negative electrode material of the part coating of one side surface in portion is 15-40 μm.
10. a kind of hybrid super capacitor, which includes positive plate, negative electrode tab, diaphragm and electrolyte, spy
Sign is that the negative electrode tab is negative electrode tab described in claim 8 or 9.
11. capacitor according to claim 10, wherein the positive plate includes positive core and its at least side table
The positive electrode of the part coating in face, the positive electrode contain conductive agent B, binder B and electric double layer energy storage material, Yi Jisuo
Stating electric double layer energy storage material is one of active carbon, graphene, carbon nanotube and carbon aerogels or a variety of.
12. capacitor according to claim 11, wherein on the basis of the total weight of the positive electrode, the conduction
The content of agent B is 5-20 weight %, and the content of the binder B is 3-10 weight %, the content of the electric double layer energy storage material
For 70-92 weight %.
13. the capacitor according to claim 8 or 11, wherein the positive plate it is with a thickness of 40-70 μm and described
The applied thickness of the positive electrode of the part coating of one side surface of positive core is 20-50 μm.
14. capacitor according to claim 8, wherein the diaphragm is polyethene microporous membrane, microporous polypropylene membrane, nothing
One of machine ceramic membrane and paper diaphragm are a variety of.
15. capacitor according to claim 8, wherein the solvent in the electrolyte is acetonitrile, and solute is hexafluorophosphoric acid
Lithium, and the concentration of the solute is 0.8-1.2mol/L and the ionic conductivity of the electrolyte is 50-60mS/cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711017872.9A CN109727784A (en) | 2017-10-27 | 2017-10-27 | Lithium titanate/carbon material compound, negative electrode material, negative electrode tab and hybrid super capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711017872.9A CN109727784A (en) | 2017-10-27 | 2017-10-27 | Lithium titanate/carbon material compound, negative electrode material, negative electrode tab and hybrid super capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109727784A true CN109727784A (en) | 2019-05-07 |
Family
ID=66290565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711017872.9A Pending CN109727784A (en) | 2017-10-27 | 2017-10-27 | Lithium titanate/carbon material compound, negative electrode material, negative electrode tab and hybrid super capacitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109727784A (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101404210A (en) * | 2008-11-19 | 2009-04-08 | 中国船舶重工集团公司第七一二研究所 | High-power super capacitor |
| CN102130324A (en) * | 2011-01-05 | 2011-07-20 | 上海大学 | Preparation method of lithium titanate/carbon nano tube composite cathode material |
| CN103022459A (en) * | 2012-11-27 | 2013-04-03 | 中国科学院大连化学物理研究所 | Preparation method of graphene/lithium titanate composite anode material |
| CN103646788A (en) * | 2013-12-19 | 2014-03-19 | 山东大学 | Nickel oxalate based asymmetrical supercapacitor and preparation method thereof |
| CN104103823A (en) * | 2014-07-09 | 2014-10-15 | 同济大学 | Preparation method of layered Li4Ti5O12@graphene composite lithium ion battery anode material |
| CN105405674A (en) * | 2015-12-14 | 2016-03-16 | 中南大学 | Transition metal high-valence oxide electrode and preparation method and application thereof |
| CN105428086A (en) * | 2015-11-11 | 2016-03-23 | 湖北诺邦科技股份有限公司 | Lithium-ion super capacitor electrolyte |
| CN106504900A (en) * | 2015-09-04 | 2017-03-15 | 罗伯特·博世有限公司 | Asymmetrical hybrid super capacitor |
| CN106504912A (en) * | 2015-09-04 | 2017-03-15 | 罗伯特·博世有限公司 | hybrid super capacitor |
| CN106848251A (en) * | 2017-03-15 | 2017-06-13 | 北京朗盛特耐科技有限公司 | A kind of preparation method of CNT lithium titanate composite anode material |
| CN107226454A (en) * | 2017-07-14 | 2017-10-03 | 东莞市迈科科技有限公司 | A kind of preparation method of lithium titanate graphene composite negative pole |
-
2017
- 2017-10-27 CN CN201711017872.9A patent/CN109727784A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101404210A (en) * | 2008-11-19 | 2009-04-08 | 中国船舶重工集团公司第七一二研究所 | High-power super capacitor |
| CN102130324A (en) * | 2011-01-05 | 2011-07-20 | 上海大学 | Preparation method of lithium titanate/carbon nano tube composite cathode material |
| CN103022459A (en) * | 2012-11-27 | 2013-04-03 | 中国科学院大连化学物理研究所 | Preparation method of graphene/lithium titanate composite anode material |
| CN103646788A (en) * | 2013-12-19 | 2014-03-19 | 山东大学 | Nickel oxalate based asymmetrical supercapacitor and preparation method thereof |
| CN104103823A (en) * | 2014-07-09 | 2014-10-15 | 同济大学 | Preparation method of layered Li4Ti5O12@graphene composite lithium ion battery anode material |
| CN106504900A (en) * | 2015-09-04 | 2017-03-15 | 罗伯特·博世有限公司 | Asymmetrical hybrid super capacitor |
| CN106504912A (en) * | 2015-09-04 | 2017-03-15 | 罗伯特·博世有限公司 | hybrid super capacitor |
| CN105428086A (en) * | 2015-11-11 | 2016-03-23 | 湖北诺邦科技股份有限公司 | Lithium-ion super capacitor electrolyte |
| CN105405674A (en) * | 2015-12-14 | 2016-03-16 | 中南大学 | Transition metal high-valence oxide electrode and preparation method and application thereof |
| CN106848251A (en) * | 2017-03-15 | 2017-06-13 | 北京朗盛特耐科技有限公司 | A kind of preparation method of CNT lithium titanate composite anode material |
| CN107226454A (en) * | 2017-07-14 | 2017-10-03 | 东莞市迈科科技有限公司 | A kind of preparation method of lithium titanate graphene composite negative pole |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2018533174A (en) | High nickel positive electrode material for lithium ion batteries coated with modified superhydrophobic material and method for preparing the same | |
| CN110311092B (en) | SnO (stannic oxide)2carbon/V2O5Application of/graphene composite nano material as battery negative electrode material | |
| CN106745323B (en) | A kind of preparation method of iron sulphur compound and its composite material | |
| CN106129377B (en) | A kind of preparation method of sesquioxide/graphene composite material, negative electrode of lithium ion battery, lithium ion battery | |
| CN106229503B (en) | A kind of preparation method of nickel oxide/graphene nanocomposite material, negative electrode of lithium ion battery, lithium ion battery | |
| CN104157858B (en) | Classifying porous ferroso-ferric oxide/graphene nano line and its preparation method and application | |
| CN107317014A (en) | The Fe of FeS claddings3O4Nano composite material and its application | |
| CN103123967A (en) | SiO/C composite cathode material of lithium ion battery and preparation method of SiO/C composite cathode material | |
| CN108390037A (en) | A kind of nickelic anode material of lithium battery of silica-graphene coated and preparation method | |
| CN104993110B (en) | A kind of preparation method of composite negative electrode material of lithium ion battery | |
| CN108807008A (en) | A kind of lithium-ion capacitor nano whiskers flexibility lithium titanate/carbon nano tube/graphene composite material and preparation method | |
| CN108878154A (en) | The preparation method of sodium titanate nano-fiber material and using the material as the sodium ion mixed capacitor of cathode | |
| CN109473659A (en) | A kind of polypyrrole nanotube/Co3O4Particulate composite and preparation method | |
| CN109616331A (en) | A kind of hud typed nickel hydroxide nano piece/manganese cobalt/cobalt oxide combination electrode material and preparation method thereof | |
| CN107359345A (en) | A kind of preparation method and applications of cornstarch porous carbon@graphite | |
| CN107681147A (en) | A kind of preparation method of solid electrolyte coating modification anode material for lithium-ion batteries and application | |
| CN111785946B (en) | Negative active material, preparation and application thereof | |
| CN109659521A (en) | A kind of preparation method of high-performance sodium-ion battery vanadic anhydride/grapheme composite positive electrode material | |
| CN110838583A (en) | Carbon nanotube/M-phase vanadium dioxide composite structure, preparation method thereof and application thereof in water-based zinc ion battery | |
| CN110415994A (en) | A kind of electrochemical energy storage three-dimensional manometer combination electrode material and preparation method thereof | |
| CN104752073A (en) | Preparation method of ferromanganese oxide/carbon composite materials | |
| CN112421017A (en) | Preparation method of binder-free water-based zinc ion battery positive electrode composite material | |
| Chen et al. | High-performanced flexible solid supercapacitor based on the hierarchical MnCo2O4 micro-flower | |
| CN108682564B (en) | A kind of Ni-C composite material and preparation method for supercapacitor | |
| CN105957724A (en) | Asymmetrical supercapacitor and preparation method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190705 Address after: 102402 No. 168 Linlin East Street, Liu Pingzhuang Village, Doudian Town, Fangshan District, Beijing Applicant after: MATERIAL AND INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE BEIJING Address before: 102400 room 4, 4 floor, 2 building, 85 Hong Yuan Road, Fangshan District, Beijing. Applicant before: Beijing carbon sun Technology Co., Ltd. |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190507 |