CN110299529A - Negative electrode material, negative electrode tab, battery component and preparation method - Google Patents
Negative electrode material, negative electrode tab, battery component and preparation method Download PDFInfo
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- CN110299529A CN110299529A CN201910627037.XA CN201910627037A CN110299529A CN 110299529 A CN110299529 A CN 110299529A CN 201910627037 A CN201910627037 A CN 201910627037A CN 110299529 A CN110299529 A CN 110299529A
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- negative electrode
- mxene
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- electrode material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to negative electrode material, negative electrode tab, battery component and preparation methods.Negative electrode material disclosed by the invention, comprising: MXene, MXene are in stratiform, and are the main body of negative electrode material；Graphene, graphene are inserted into MXene interlayer with intercalated form.Negative electrode tab disclosed by the invention includes negative electrode material of the invention.Battery component disclosed by the invention includes diaphragm and the negative electrode tab of the invention that is attached on diaphragm.The preparation method of negative electrode material disclosed by the invention, comprising steps of S1: at 0~30 DEG C, after graphene dispersing solution to be added to the dispersion liquid of MXene, carrying out ultrasound in an inert atmosphere, obtain suspension；S2: the solvent in suspension is removed to get negative electrode material is arrived.The preparation method of negative electrode tab disclosed by the invention in step s 2 takes film layer off after filtering drying to obtain the final product.The preparation method of battery component disclosed by the invention, in step s 2, suction filtration film are battery diaphragm, after suction filtration is dry to obtain the final product.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular to a kind of negative electrode material, negative electrode tab, battery component and preparation side
Method.
Background technique
With the development of mancarried electronic aid, electric car and wearable device, performance requirement of the people to energy storage device
It is higher and higher.
The battery capacity and high rate performance of current battery are less able to satisfy demand, MXene because have biggish specific surface area,
Lesser ion transmission path without binder and is exempted to be coated with, and the capacity and high rate performance of battery can be improved, and receive pass
Note.
MXene is a kind of newer two-dimensional material, generally with formula Mn+1XnTxIt indicates, wherein M represents transition metal member
Element, X (capitalization) are carbon and/or nitrogen, and T represents the functional group (such as :-F and-OH) that MXene is generated during the preparation process, and n is general
It is 1~4.X (small letter) refers to that number of functional groups is related with the etching preparation process of MXene, and x is uncertain value.
But MXene exists following insufficient: the first, MXene between layers since there are Van der Waals force, Yi Fasheng is collapsed
And stacking, therefore when by it separately as negative electrode material, it is easy to increase ion diffusional resistance because collapsing with stacking, keeps cathode living
Property site reduce or cathode failure, when it is used for lithium battery, the battery capacity and high rate performance of lithium battery can be reduced；The second,
The mechanical performance of MXene is poor, when individually using MXene as negative electrode material, easy fragmentation, it is difficult to form complete film layer.
Summary of the invention
(1) technical problems to be solved
The present invention provides a kind of negative electrode material, by graphene with the interlayer of intercalated form insertion MXene, solves MXene
Collapsing and the problem of stacking, while also solving the technical issues of bad mechanical property of MXene between layers.
The present invention also provides the negative electrode tabs comprising negative electrode material of the present invention, battery component and preparation method thereof.
(2) technical solution
According to an aspect of the present invention, a kind of negative electrode material is provided, comprising:
MXene, the MXene are in stratiform, and are the main body of the negative electrode material；
Graphene, the graphene are inserted into the interlayer of the MXene with intercalated form.
Optionally, negative electrode material according to the present invention, the mass ratio of the MXene and the graphene be 1:0.1~
0.8。
Optionally, negative electrode material according to the present invention further includes carbon nanotube, and the carbon nanotube is through described
The interlayer that MXene and the graphene are formed.
Optionally, negative electrode material according to the present invention, the mass ratio of the MXene and the carbon nanotube be 1:0.03~
0.1。
According to another aspect of the present invention, a kind of negative electrode tab is provided, the negative electrode tab includes negative electrode material of the invention.
Optionally, negative electrode tab according to the present invention, the negative electrode tab is the film layer that negative electrode material of the invention is constituted, in institute
The quality accounting for stating negative electrode material described in film layer is 100%；
Optionally, negative electrode tab according to the present invention, the film layer with a thickness of 5~25um.
According to another aspect of the present invention, a kind of battery component is provided, it is described including diaphragm and negative electrode tab of the invention
Negative electrode tab is attached to the diaphragm.
According to another aspect of the present invention, a kind of preparation method of negative electrode material is provided, comprising steps of
S1: at 0~30 DEG C, after graphene dispersing solution to be added to the dispersion liquid of MXene, carrying out ultrasound in an inert atmosphere,
Obtain suspension；
S2: the solvent in the suspension is removed to get the negative electrode material is arrived.
Optionally, preparation method according to the present invention is also added into carbon containing in the dispersion liquid of MXene in step sl
The dispersion liquid of nanotube.
Optionally, preparation method according to the present invention, the quality of the MXene, the graphene and the carbon nanotube
Than for 1:0.1~0.8:0.03~0.1.
According to another aspect of the present invention, a kind of preparation method of negative electrode tab is provided, in step S2, described in removal
Solvent in suspension is that dry 3 under the conditions of 0~30 DEG C~for 24 hours, obtained film layer is taken off up to cathode after suction filtration
Piece.
According to another aspect of the present invention, a kind of preparation method of battery component is provided, in step s 2, removes institute
State the solvent in suspension, be when filtering, suctions filtration film is diaphragm, after suction filtration at 0~30 DEG C dry 3~for 24 hours to get described in arriving
Battery component；Wherein,
The battery component includes diaphragm and the negative electrode tab for being attached to the diaphragm.
(3) beneficial effect
(1) negative electrode material of the invention, graphene insert MXene interlayer as intercalation, on the one hand, prevent MXene
Interlayer collapse and stacking, negative electrode material of the invention is used for battery, then reduces ion diffusional resistance, is released more
Active site improves battery capacity and high rate performance；On the other hand, since graphene belongs to sp2 type hydridization, mechanical strength
Higher, the addition of graphene improves the mechanical performance of negative electrode material, thus make its have when preparing negative electrode tab it is good at
Film properties, and make the negative electrode tab being prepared that there is good mechanical performance.
(2) in negative electrode material of the present invention, further preferably carbon nanotube is formed through graphene and MXene
Interlayer.
On the one hand, the interlayer that carbon nanotube is formed through graphene and MXene, can play a supporting role to each layer,
It prevents interlayer from collapsing and stacking, negative electrode material of the present invention is used for battery, then reduces ion diffusional resistance, releases more
More active sites improves the capacity and high rate performance of battery；On the other hand, the electric conductivity of carbon nanotube itself is good, and
It constructs three-dimensional conductive network in negative electrode material, improves the electric conductivity of negative electrode material, when being used for lithium battery, then
Improve the high rate performance of battery.
(3) negative electrode tab of the invention when being used for lithium battery, can be improved due to containing negative electrode material of the invention
The battery capacity and high rate performance of lithium battery.
It, will due to not containing collector, conductive agent and binder etc. in the negative electrode tab for only containing negative electrode material of the invention
It is used for lithium battery, and the battery capacity of lithium battery can be improved；And the negative electrode tab has good mechanical performance.
(4) battery component of the invention includes diaphragm and negative electrode tab, has both had the excellent performance of above-mentioned pole piece, while can
With directly by the component assembled battery, to reduce assembling steps.
(5) preparation method of negative electrode material according to the present invention, can prepare negative electrode material of the invention.
(6) film layer is removed down after removing solvent using dry removal solvent is filtered in the removal solvent step of step S2
Come, needs cutting to can be obtained by negative electrode tab according to specification.
(7) when removing solvent in step s 2, using the dry removal solvent of suction filtration, suction filtration film is diaphragm, after filtering drying
Obtain battery component, specification as needed cuts the available battery component including diaphragm and negative electrode tab, can directly by
Battery component is used for battery assembly, shortens the processing step of battery assembly.
Detailed description of the invention
Figure 1A is the micromodel figure of MXene；
Figure 1B is the negative electrode material micromodel figure including graphene and MXene of the invention；
Fig. 1 C is the negative electrode material micromodel figure including carbon nanotube, graphene and MXene of the invention.
Fig. 2 is the Ti of acid etch used in the examples removing3C2TxSEM figure.
Fig. 3 is the SEM figure for the negative electrode tab that embodiment 2 is prepared.
Fig. 4 is the photo for the negative electrode tab that embodiment 2 is prepared.
Appended drawing reference:
1:MXene, 2: graphene intercalation, 3: carbon nanotube, 4: negative electrode tab.
Specific embodiment
In order to preferably explain the present invention, in order to understand, with reference to the accompanying drawing and embodiment, the present invention is carried out detailed
Thin description.
According to an aspect of the present invention, a kind of negative electrode material is provided, comprising: MXene, MXene are in stratiform, and are negative
The main body of pole material；Graphene, graphene is with the interlayer of intercalated form insertion MXene.
Negative electrode material of the invention, graphene insert MXene interlayer as intercalation, on the one hand, prevent MXene interlayer
Collapse and stacking, negative electrode material of the invention is used for battery, then reduces ion diffusional resistance, releases more activity
Site improves battery capacity and high rate performance；On the other hand, since graphene belongs to sp2 type hydridization, mechanical strength compared with
The addition of height, graphene improves the mechanical performance of negative electrode material, so that it be made to have good film forming when preparing negative electrode tab
Performance, and make the negative electrode tab being prepared that there is good mechanical performance.
Wherein, Ti can be selected in MXene3C2Tx、Ti2CTx、V2CTx、Cr2CTxAt least one of, wherein T be-F ,-OH and-
One or more of O, x are the quantity of functional group, and it is uncertain numerical value.Wherein-O is formed on the surface MXene
Functional group, i.e., not formed chemical bond, but since electrostatic adsorption makes MXene adsorption oxygen atom.
Wherein, the stratiform as shown in Fig. 1 (A) is presented in MXene (1).
In negative electrode material of the invention, form with graphene intercalation 2 of the graphene layer 2 as shown in Fig. 1 (B) is inserted into
The interlayer of MXene (1).
It is worth noting that Fig. 1 (A) and Fig. 1 (B) are illustraton of model, actual microgram box model may not be illustrated
Rule out.
Wherein, MXene is the main body of negative electrode material, is referred in negative electrode material, the quality accounting of MXene is higher than graphite
Alkene, or it is higher than graphene and carbon nanotube, its quality accounting can be higher than other materials in a word.
The mass ratio of some embodiments of negative electrode material according to the present invention, MXene and graphene is 1:0.1~0.8.
The mass ratio of MXene and graphene is typical but preferred without limitation 1:0.1,1:0.2,1:0.3,1:0.4,1:
0.5,1:0.6,1:0.7 and 1:0.8.
When the mass ratio of MXene and graphene is less than 1:0.1, on the one hand, cannot be effective since graphene accounting is lower
Solve the problems, such as that MXene interlayer collapses and stacking；On the other hand, since graphene accounting is the bottom of compared with, cathode material cannot be effectively improved
The mechanical performance of material makes negative electrode material film forming difference that cannot even form a film.
When the mass ratio of MXene and graphene is greater than 1:0.8, on the one hand, since graphene accounting is excessively high, MXene is made to exist
The opposite reduction of accounting in negative electrode material, reduces negative electrode material conductivity, so that the high rate performance of battery can be reduced；Another party
Face, graphene are also layer structure, and the accounting of graphene is excessively high, can also be collapsed and stacking, and then can reduce battery
Capacity.
Some embodiments of negative electrode material according to the present invention, further include carbon nanotube, and carbon nanotube is through MXene
The interlayer formed with graphene.
On the one hand, the interlayer that carbon nanotube is formed through graphene and MXene, can play a supporting role to each layer,
It prevents interlayer from collapsing and stacking, negative electrode material of the present invention is used for battery, then reduces ion diffusional resistance, releases more
More active sites improves the capacity and high rate performance of battery；On the other hand, the electric conductivity of carbon nanotube itself is good, and
It constructs three-dimensional conductive network in negative electrode material, improves the electric conductivity of negative electrode material, when being used for lithium battery, then
Improve the high rate performance of battery.
Wherein, the interlayer that MXene is formed with the graphene includes but is not limited to: the interlayer that MXene and graphene are formed,
The interlayer that the interlayer that MXene and MXene is formed, graphene and graphene are formed.
Wherein, perforative form is not limited to extend vertically through in interlayer, can be with since carbon nanotube is one-dimensional tubulose
Intersect for a plurality of carbon nanotube through multiple interlayers, or carbon nanotube bending intersect through etc. forms, it is right herein
Through form and without limitation, and its a plurality of carbon nanotube can be ordered into and run through, or and it is unordered to run through, run through form
Depend entirely on the randomness in preparation process.
Fig. 1 (C) shows the interlayer that carbon nanotube is formed through MXene and graphene.
The mass ratio of some embodiments of negative electrode material according to the present invention, MXene and carbon nanotube be 1:0.03~
0.1。
Wherein, MXene and carbon nanotube mass than typical but preferred without limitation 1:0.03,1:0.04,1:0.05,
1:0.06,1:0.07,1:0.08,1:0.09 and 1:0.1.
When MXene and carbon nanotube mass ratio are less than 1:0.03, on the one hand, the accounting of carbon nanotube is lower, to each layer
Support effect it is unobvious, not can be well solved and collapse and stacking problem；On the other hand, the accounting of carbon nanotube is lower, meeting
Making the electric conductivity of negative electrode material reduces.
If the ratio between MXene and carbon nanotube mass are greater than 1:0.1, on the one hand, the ratio of carbon nanotube is excessively high, carbon nanotube
Itself capacity is not provided, therefore reduces the capacity of battery；On the other hand, the ratio of carbon nanotube is excessively high, its own can occur
Reunite, to reduce the high rate performance of battery.
According to another aspect of the present invention, a kind of negative electrode tab is provided, negative electrode tab includes negative electrode material of the invention.
A kind of embodiment of negative electrode tab of the invention be include collector, negative electrode material of the invention, conductive agent and
The negative electrode tab of binder.It is that negative electrode tab is prepared according to traditional pole piece manufacture craft, i.e., in negative current collector (such as copper
Foil) it is dry after surface coating slurry made of negative electrode material of the invention, conductive agent and binder made from negative electrode tab.Wherein
Negative current collector type, the type of conductive agent and dosage, the type of binder and dosage can be carried out according to conventional selection.
The negative electrode tab due to use negative electrode material of the invention, equally solve the problems, such as MXene collapse and stacking,
It equally solves the problems, such as the bad battery that is not easy to form a film, be prepared using the negative electrode tab of its mechanical performance, and only uses MXene
Battery (other conditions of the two are all the same, and difference is only that the selection of negative electrode material is different) as negative electrode material is compared, and is mentioned
The high capacity and high rate performance of battery.
In another embodiment of the present invention, negative electrode tab is to be prepared completely by negative electrode material of the invention；I.e. not
Include collector, binder and conductive agent.
On the one hand, which does not include collector, conductive agent and binder, and the battery capacity comprising its battery can be more
It is high；On the other hand the satisfactory mechanical property of the negative electrode tab.
A kind of embodiment of negative electrode tab according to the present invention, negative electrode tab are the film layer that negative electrode material of the invention is constituted,
The quality accounting of the negative electrode material described in film layer is 100%.
The embodiment is the above-mentioned negative electrode tab not comprising collector, binder and conductive agent.
Some embodiments of negative electrode tab according to the present invention, film layer with a thickness of 5~25um.
Wherein the thickness of film layer is typical but preferred without limitation 5um, 8um, 10um, 12um, 15um, 18um, 20um,
22um and 25um.
According to another aspect of the present invention, a kind of battery component is provided, including diaphragm and negative electrode tab of the invention, cathode
Piece is attached to diaphragm.
Battery component of the invention includes diaphragm and negative electrode tab, has both had an excellent performance of above-mentioned pole piece, while can be with
Directly by the component assembled battery, to reduce assembling steps.
According to another aspect of the present invention, a kind of preparation method of negative electrode material is provided, comprising steps of
S1: at 0~30 DEG C, after graphene dispersing solution to be added to the dispersion liquid of MXene, carrying out ultrasound in an inert atmosphere,
Obtain suspension；
S2: the solvent in the suspension is removed to get the negative electrode material is arrived.
The preparation method of negative electrode material according to the present invention can prepare negative electrode material of the invention, and what is be prepared is negative
Pole material can solve the stacking of MXene and collapse problem, and it is bad also to can solve its mechanical performance, be not easy the problem of forming a film.
Wherein, in step sl temperature is preferably 0 DEG C typical but non-limiting, 3 DEG C, 5 DEG C, 8 DEG C, 10 DEG C, 13 DEG C,
15 DEG C, 18 DEG C, 20 DEG C, 23 DEG C, 25 DEG C, 28 DEG C and 30 DEG C.
Since MXene is under conditions of having water aerobic, when being greater than 30 DEG C, easily aoxidize；When less than 0 DEG C, it is unfavorable for stone
Black alkene is inserted into MXene interlayer；It is aoxidized in order to prevent, and graphene can be made preferably to be inserted into MXene interlayer, by temperature
Control is at 0~30 DEG C.
Wherein, in the graphene dispersing solution selected under normal circumstances, the solid content of graphene is 0.2~0.33mg/ml,
The solid content of MXene is 3~5mg/ml；The speed that graphene dispersing solution is added in MXene dispersion liquid is preferably 30~50ml/
Min is usually added while stirring, so that the two is uniformly dispersed, the preferred 100-260r/min of mixing speed, mixing time is preferred
20-50min。
Wherein, inert atmosphere can select conventional inert gas, such as argon gas.
MXene and graphene in the liquid phase, realize microcosmic mixing under ultrasonication, and ultrasonic wave acts on solid liquid interface production
The microjet of raw moment cavity and moment impact solid phase surface, the MXene for being conducive to stratiform intert mutually with graphene, due to
The quality of MXene accounts for relatively high, therefore graphene is in the process, the interlayer as intercalation insertion MXene.
Wherein, in step s 2 ultrasonic frequency preferred 10-20KHZ, typical but preferred without limitation 10KHZ,
12KHZ, 15KHZ, 18KHZ and 20KHZ.
Ultrasonic time preferred 15-30min, typical but preferred without limitation 15min, 18min, 20min, 23min,
25min, 28min and 30min.
Preferably 0~30 DEG C of ultrasound environments temperature, it is typical but without limitation preferably 0 DEG C, 5 DEG C, 10 DEG C, 15 DEG C, 20 DEG C,
25℃、30℃。
When preparing negative electrode material of the present invention, MXene used can be used any prior art preparation and obtain.
But the MXene dispersion liquid being used in the present invention is by the way that the progress acid etching of MAX phase ceramics powder to be prepared
's.Its general operation are as follows: MAX phase ceramics powder is added in dense HF solution, carries out acid etch reaction at a certain temperature, instead
Solution ethyl alcohol and/or deionized water after answering wash away spent acid using centrifugal process, obtain the dispersion liquid of MXene.MAX phase ceramics powder
Body selects Ti3AlC2、Ti2AlC、V2AlC、Cr2At least one of AlC.(residual HF can lose the dispersion liquid plastic bottle of MXene
Glassware) it collects, argon gas is passed through in bottle and is sealed, it is stored refrigerated.
The MXene dispersion liquid used in embodiments of the present invention specific the preparation method is as follows:
Step 1: hydrofluoride being added in reactor, concentrated hydrochloric acid is added and is stirred to react, prepares hydrofluoric acid solution, hydrogen fluorine
Sour mass concentration is 40~50%.Preferably, hydrofluoride is lithium fluoride, sodium fluoride or potassium fluoride；Concentrated hydrochloric acid is mass concentration
38% or more hydrochloric acid.Stirring uses magnetic stirring apparatus, and revolving speed is that 200-500r/min is stirred 5-7 minutes.
Step 2: by MAX phase ceramics powder with it is a small amount of, be repeatedly added in reactor, it is stirring while adding, make MAX phase ceramics
Powder is completely dissolved in a solution of hydrofluoric acid, is then kept the temperature in reactor at 35-50 DEG C, is stirred to react 20-30h.MAX
After phase ceramics powder is added, speed of agitator is that 300-600r/min is stirred 5-10 minutes.After the dissolution of MAX phase ceramics powder, in 35
Speed of agitator is 200-300r/min under DEG C constant temperature, is stirred to react for 24 hours.
Step 3: using centrifugal process to wash reaction solution ethyl alcohol and/or deionized water to remove demineralizing acid, hydrofluoric acid and chlorine
Change lithium, shakes centrifugation after suitable water is added in the solid that centrifugation obtains, centrifugal rotational speed is not more than 6000r/min, by upper layer
Blackish green dispersion liquid is separated, and argon gas-sealed is collected in plastic bottle and is passed through, and is refrigerated spare.
When preparing negative electrode material of the present invention, can be used natural graphite alkene be dissolved in deionized water or ethyl alcohol equal solvent prepare and
At；It can also be using the method that is by mechanically pulling off, Hummers method, improved Hummers method, the preparation of ultrasonic wave added Hummers method
Graphene oxide dispersion.It is not excessive when using graphene oxide as raw material, it, need to be to oxidation stone when obtaining final negative electrode material
Black alkene is restored, and to obtain negative electrode material of the invention, and the opposite negative electrode material containing graphene oxide improves conductivity.
The method for removing solvent in step s 2 can use a variety of different approach.
MXene may be oxidized when can select the mode of drying, but dry, and not use which as far as possible generally.
Desivac can also be used, the negative electrode material obtained after freeze-drying is powdered, the graphene insertion in microstructure
Arrived MXene interlayer, equally solve the problems, such as MXene collapse and stacking and the poor problem of MXene mechanical performance.
But when preparing negative electrode tab using the powdered negative electrode material of freeze-drying, it need to be made up of conventional method containing powdered negative
Pole material, binder, solvent, conductive agent slurry, by slurry be coated on collector it is dry after negative electrode tab is made.
Film layer can be obtained using seasoning is filtered, adjustable obtained thicknesses of layers during suction filtration, by film
Layer is stripped out, and specification as needed is cut out both available negative electrode tabs, since the film layer is entirely negative electrode material structure
At, therefore it is also a kind of existence of negative electrode material.
Can be directly as negative electrode tab using the film layer for filtering seasoning acquisition, which does not depend on collector presence,
And conductive agent and binder are free of, the accounting of negative electrode material is greatly improved, to improve the capacity of lithium battery.
Preparation method according to the present invention is also added into carbon nanotubes in the dispersion liquid of MXene in step sl
Dispersion liquid.
In the preparation method of negative electrode material of the present invention, the dispersion of carbon nanotubes joined in the dispersion liquid of MXene
Liquid is made and has run through the negative electrode material of carbon nanotube in each interlayer of negative electrode material.
Wherein, in the dispersion liquid of carbon nanotubes, the solid content of carbon nanotube is 0.03~0.07mg/ml.
MXene, graphene and carbon nanotube in the liquid phase, microcosmic mixing is carried out under ultrasonication, ultrasonic wave acts on
Solid liquid interface generates moment cavity and impacts the microjet of solid phase surface, enhances solid phase mass transfer, improves solid phase surface activity, no
Intert the MXene of stratiform mutually with graphene, forms the carbon nanotube of threadiness through MXene and graphene
Between each layer.
A kind of embodiment of method produced according to the present invention, the mass ratio of MXene, graphene and carbon nanotube preferably 1:
0.1~0.8:0.03~0.1.
The mass ratio of MXene, graphene and carbon nanotube is typical but preferred without limitation 1:0.1:0.03,1:0.1:
0.05,1:0.1:0.08,1:0.1:0.1,1:0.2:0.03,1:0.2:0.05,1:0.2:0.1,1:0.3:0.03,1:0.3:
0.05,1:0.3:0.1,1:0.5:0.03,1:0.5:0.8,1:0.5:0.1,1:0.8:0.03,1:0.8:0.05,1:0.8:
0.1。
According to another aspect of the present invention, a kind of preparation method of negative electrode tab is provided, in step S2, removal suspends
Solvent in liquid is after filtering under an inert atmosphere, after suction filtration dry 3 under the conditions of inert atmosphere and 0~30 DEG C~for 24 hours, will
Obtained film layer is taken off up to negative electrode tab.
Wherein, the preferred argon gas of inert atmosphere；Temperature it is typical but without limitation preferably 0 DEG C, 4 DEG C, 5 DEG C, 10 DEG C, 12 DEG C,
15 DEG C, 18 DEG C, 20 DEG C, 23 DEG C, 25 DEG C, 28 DEG C and 30 DEG C.
Wherein, drying time is typical but preferred without limitation 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h,
13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h and for 24 hours.
Obtained film layer will be filtered to take off to obtain negative electrode tab, collector, conductive agent and binder are free of in negative electrode tab, and have
It is flexible, can be bent；It since its flexibility is good, can be bent, the battery being more suitable in wearable device.
Wherein, those skilled in the art are controlled in combination with the solid content in the bore of suction funnel, suction filtration liquid measure, smoke filtrate
The negative electrode tab thickness of system and adjusting to be needed.
Wherein, since MXene and graphene are two-dimensional layer film, when filtering, what two-dimensional layer film layer can be spontaneous is taken
To rule, filming performance is good.
According to another aspect of the present invention, a kind of preparation method of battery component is provided, in step s 2, removal is outstanding
Solvent in supernatant liquid is to filter under an inert atmosphere, and suction filtration film is diaphragm, after suction filtration under the conditions of inert atmosphere and 0~30 DEG C
Dry 3~for 24 hours to get arriving battery component；Wherein, battery component includes diaphragm and the negative electrode tab for being attached to diaphragm.
Wherein, diaphragm can according to need any diaphragm selected and selected in lithium battery, such as select diaphragm Celgard.
Preparation method of the invention has directly obtained the component of negative electrode tab and diaphragm composition, does not need that cathode is prepared separately
Piece assembles negative electrode tab and diaphragm, says and simplifies processing step, has saved production time and cost.
In the battery component that the method for the present invention is prepared, negative electrode tab is free of collector, conductive agent and binder, improves
The battery capacity of lithium battery.
It should be noted that if in the method for preparation negative electrode material, negative electrode tab and battery component, with graphene oxide generation
For graphene, then need increase to graphene oxide reduction treatment step, so that it is reduced to graphene, with improve negative electrode material,
The conductivity of negative electrode tab in negative electrode tab and battery component.Conversely, being then not necessarily to carry out the also original place of graphene according to graphene
Reason.
Such as: graphene oxide dispersion is prepared using modified Hummers method, specifically: 1g natural graphite powder is set
In the 25ml concentrated sulfuric acid, device is placed in ice-water bath by stirring while is cooled to 0 DEG C, and 3.5g Gao Meng is slowly added wherein
Sour potassium, slowly stirring is until being uniformly mixed, and then 35 DEG C stirring in water bath 2 hours, are then added 100mL deionized water and (pay attention to
Speed is added, prevents temperature is excessively high need to be added at a slow speed), 30% hydrogen peroxide of 8mL is added, solution will be by colour of loess discoloration at this time
At light yellow.It is respectively washed with dilute hydrochloric acid and deionized water, obtains that graphene oxide water solution is stand-by, and concentration is about 6mg/mL.
After having carried out step S2 using the graphene oxide solution, dry film layer will be filtered and taken off from film layer is filtered
Afterwards, 300 DEG C are placed in vacuum drying oven to heat 8 hours, graphene oxide is heat-treated as graphene.
To further illustrate technical solution of the present invention, it is illustrated below in conjunction with specific embodiments, is worth explanation
, embodiment is only used for that the present invention will be described, without limiting protection scope of the present invention.
MXene is Ti in the following embodiments3C2Tx, Ti3C2TxThe specific preparation process of dispersion liquid is as follows.
It is prepared using the method for acid etch, raw material Ti3AlC2。
1gLiF is added in small ball grinder, the concentrated hydrochloric acid of 10mL is added into ball grinder, is stirred in the magnetic force of 500r/min
It mixes and is stirred 5 minutes under speed, continued with 200r min-1Revolving speed stirring, while stirring by the Ti of 1g3AlC2On a small quantity, repeatedly add
Enter in small ball grinder and (is about when addition 10 minutes).
After adding material, revolving speed is turned up and continues to stir 5-10 minutes to 500r/min, to Ti3AlC2By bead after being completely dissolved
Grinding jar is transferred in 35 DEG C of water-bath, is stirred and is heated 24 hours.
The solution prepared ethyl alcohol or deionized water centrifuge washing remove spent acid (hydrofluoric acid, hydrochloric acid, lithium chloride), are separating
Centrifugation is shaken after suitable water is added in obtained solid, centrifugal rotational speed is not more than 6000r/min, isolates upper layer dispersion liquid,
Obtain blackish green dispersion liquid (Ti3C2TxDispersion liquid), solid content be (3~5mg/ml) collect into plastic bottle, into plastic bottle
It is passed through argon gas and seals, be placed in stored refrigerated in refrigerator.
Fig. 2 shows the product Ti being prepared3C2TxSEM figure, as can be seen from the figure its be in lamellar structure,
In, T is the-F functional group and/or-OH functional group that preparation process introduces.
Graphene dispersing solution in the following embodiments is to be diluted to pioneer's nano-graphene slurry with deionized water
Solid content is the dispersion liquid of 1mg/mL.
Embodiment 1
In this embodiment, step S1 is carried out first: at 0~30 DEG C, graphene dispersing solution being added to the dispersion of MXene
After liquid, ultrasound is carried out in an inert atmosphere, obtains suspension；Concrete operations are as follows:
Take Ti3C2TxDispersion liquid (the Ti containing 100mg3C2Tx) in 500ml beaker, (control temperature is placed in ice water bath environment
Degree is lower than 10 DEG C) the dilute dispersion liquid of the graphene prepared (graphene containing 20mg) is slowly added thereto while stirring, it stirs
Solution is passed through argon gas protection in ultrasound 20 minutes at 20KHZ simultaneously, and controls ultrasound environments temperature and be not higher than 25 DEG C by 15min,
Obtain suspension.
Wherein, Ti3C2TxMass ratio with graphene is 1:0.2.
Then it carries out S2: removing the solvent in suspension to get negative electrode material is arrived.
Open Vacuum filtration device, by the suspension in step S1, after filtering under an inert atmosphere under protection of argon gas and
20 DEG C of dry 10h (carrying out in drying tower) take obtained film layer up to a kind of negative electrode tab (and presence of negative electrode material off
Form), thickness is about 20 μm.
Embodiment 2
Other conditions of the embodiment and embodiment 1 are all the same, difference, are to be also added into carbon in step S1
Nanotube slurry, the solid content of the carbon nanotube in the carbon nano tube paste of addition are 5mg, the i.e. matter of MXene and carbon nanotube
Amount is than being 1:0.05.
Embodiment 3
Other conditions of the embodiment and embodiment 1 are all the same, are diaphragm Celgard in addition to filtering film, after filtering drying
Battery component is obtained, which includes diaphragm and the pole piece that is attached on diaphragm.
Embodiment 4
Other conditions of the embodiment and embodiment 2 are all the same, are diaphragm Celgard in addition to filtering film, after filtering drying
Battery component is obtained, which includes diaphragm and the pole piece that is attached on diaphragm.
Embodiment 5
Compared with Example 4, other conditions are all the same for the embodiment, only change the matter of graphene in graphene dispersing solution
It measures (10mg), makes the mass ratio 1:0.1 of MXene and graphene.
Embodiment 6
Compared with Example 4, other conditions are all the same for the embodiment, only change the matter of graphene in graphene dispersing solution
It measures (50mg), makes the mass ratio 1:0.5 of MXene and graphene.
Embodiment 7
Compared with Example 4, other conditions are all the same for the embodiment, only change the matter of graphene in graphene dispersing solution
It measures (80mg), makes the mass ratio 1:0.8 of MXene and graphene.
Embodiment 8
Compared with Example 4, other conditions are all the same for the embodiment, only change carbon nanotube in carbon nano tube dispersion liquid
Quality (3mg), make the mass ratio 1:0.03 of MXene and carbon nanotube.
Embodiment 9
Compared with Example 4, other conditions are all the same for the embodiment, only change carbon nanotube in carbon nano tube dispersion liquid
Quality (10mg), make the mass ratio 1:0.1 of MXene and carbon nanotube.
Comparative example 1
Compared with Example 4, other conditions are all the same for the comparative example, and difference is in step S1 not add graphene
Dispersion liquid and carbon nano tube dispersion liquid.
Comparative example 2
Compared with Example 4, other conditions are all the same for the embodiment, only change the matter of graphene in graphene dispersing solution
It measures (5mg), makes the mass ratio 1:0.05 of MXene and graphene.
Comparative example 3
Compared with Example 4, other conditions are all the same for the embodiment, only change the matter of graphene in graphene dispersing solution
It measures (90mg), makes the mass ratio 1:1.1 of MXene and graphene.
Comparative example 4
Compared with Example 4, other conditions are all the same for the embodiment, only change carbon nanotube in carbon nano tube dispersion liquid
Quality (2mg), make the mass ratio 1:0.02 of MXene and carbon nanotube.
Comparative example 5
Compared with Example 4, other conditions are all the same for the embodiment, only change carbon nanotube in carbon nano tube dispersion liquid
Quality (15mg), make the mass ratio 1:0.15 of MXene and carbon nanotube.
The battery component that embodiment 3~10 and comparative example 1~5 are prepared, is assembled into button cell respectively.
Battery assembly: obtained battery component is cut, and uses lithium piece to electrode, (water, oxygen are lower than in glove box
0.1ppm) assemble CR2025 model button cell.
High rate performance test, test condition are carried out to the obtained battery of assembling are as follows: current-density gradient be designed as 30mA/g,
50mA/g, 100mA/g, 200mA/g, 500mA/g and 30mA/g are recycled 10 weeks under each current-density gradient, and cycling condition is
When room temperature, the maximum capacity that the battery capacity in 10 times is recycled under each current-density gradient is taken.
That is: same battery recycles the 1st~10 time in 30mA/g, records maximum battery capacity therein；In 50mA/g
Shi Xunhuan the 11st~20 time, record maximum battery capacity therein；It recycles the 21st~30 time, records therein in 200mA/g
Maximum battery capacity；It is recycled the 31st~40 time in 500mA/g, records maximum battery capacity therein；Then in 30mA/g
It recycles the 41st~50 time, record maximum battery capacity (restores capacity).
Wherein, when battery capacity ratio with electric current is 30mA/g, it is worth at circulation 1~10 time on the basis of the maximum capacity that measures,
Such as: C50/C30 indicates, the battery maximum capacity that measures in circulation 10 times when electric current is 50mA/g, with electric current be
The ratio of the battery maximum capacity measured in circulation 10 times when electric current is 30mA/g.
It can be seen that the variation of battery high rate performance by the comparison of the ratio；It, can be with by the variation of battery capacity value
Find out the variation of battery capacity.
Wherein test result is as shown in table 1, table 2 and table 3.
Table 1
MXene layers of sheet is inserted into as intercalation by graphene it can be seen from the data comparison of 1 embodiment 3 of table and comparative example 1
Invention negative electrode material, the negative electrode material of the MXene than being not inserted into graphene improve the high rate performance and capacity of battery.This says
Bright graphene as intercalation be inserted into MXene layers, solve the problems, such as to a certain extent MXene collapse and stacking, improve electricity
The high rate performance and capacity in pond.
The battery of the embodiment 4 of carbon nanotube is added it can be seen from the data comparison of 1 embodiment 4 of table and embodiment 3
High rate performance and capacity, high rate performance and capacity than the embodiment 3 of carbon nanotube is not added increase.This explanation, is added
Carbon nanotube further solve MXene collapse with stacking problem, and also due to carbon nanotube building three-dimensional conductive network
And its own good electric conductivity, further improve the high rate performance of battery.
In addition, in comparative example 1 pure Mxene due to being to filter the component of negative electrode tab and diaphragm being prepared,
With more stable cycle performance.
Table 2
By the embodiment 5 of table 2 it is found that especially embodiment 5 is compared with comparative example 2 it is found that working as compared with comparative example 2
The mass ratio of MXene and graphene is more than or equal to the high rate performance and battery capacity that 1:0.1 improves battery.It can be seen that
When the mass ratio of MXene and graphene is greater than 1:0.1, it just can effectively solve MXene interlayer and collapse and the problem of stacking, from
And improve the high rate performance and battery capacity of battery.
By table 2 embodiment 7 and comparative example 3 compare it is found that when the mass ratio of MXene and graphene be greater than 1:0.8 when, one
Aspect makes accounting of the MXene in negative electrode material is opposite to reduce, reduces negative electrode material conductance since graphene accounting is excessively high
Rate, so that the high rate performance of battery can be reduced；On the other hand, graphene is also layer structure, and the accounting of graphene is excessively high,
It can collapse and stacking, and then the capacity of battery can be reduced.
By 4~embodiment of embodiment 7, the data of comparative example 3 it can also be seen that when Mxene and graphene mass ratio from
When 1:0.1 to 1:0.5, the high rate performance and capacity of battery are to gradually rise, when the mass ratio of Mxene and graphene is higher than 1:
When 0.5, battery capacity continues to increase, but high rate performance gradually declines, when the mass ratio of Mxene and graphene is higher than 1:0.8
When, stacking phenomenon can also occur for graphene itself, therefore battery capacity can also reduce.
Table 3
It is compared by 3 comparative example 4 of table with embodiment 8, it can be seen that when MXene and carbon nanotube mass ratio are less than 1:0.03
When, on the one hand, the accounting of carbon nanotube is lower, unobvious to the support effect of each layer, not can be well solved between each layer
It collapses and stacking problem；On the other hand, the accounting of carbon nanotube is lower, and the electric conductivity of negative electrode material can be made to reduce, therefore reduces
The high rate performance and capacity of battery.
It is compared by 3 comparative example 5 of table with embodiment 9, it can be seen that when the ratio between MXene and carbon nanotube mass are greater than 1:0.1,
On the one hand, the ratio of carbon nanotube is excessively high, and carbon nanotube itself does not provide capacity, therefore reduces the capacity of battery；Another party
The ratio in face, carbon nanotube is excessively high, its own can reunite, to reduce the high rate performance of battery.
The negative electrode tab that applicant obtains embodiment 2 has carried out SEM test, and test result, can be with by Fig. 3 as shown in Fig. 3
Find out that carbon nanotube has run through the interlayer that MXene and graphene are formed.
The negative electrode tab that applicant also obtains embodiment 2 has carried out bend test, photo is tested as shown in Fig. 4, by Fig. 4
As can be seen that the negative electrode tab that the present invention obtains has good mechanical performance, good flexibility is maintained in bending.
The battery assembled by the battery component of embodiment 4 and comparative example 1 has also been carried out cycle performance by applicant
Test, the current density of test are 30mA/g, room temperature cycles.
In addition, the battery component that comparative example 1 is prepared is during cutting, film layer edges broken and in powdered de-
It falls, complete membranoid substance can not be torn off on the corner under cutting.It can thus be appreciated that only negative electrode tab made of MXene, bad mechanical property,
Film forming is poor, and embodiment 3~10 does not occur this fragmentation in powdered the phenomenon that falling off, and can completely takes film layer off,
It can be seen that negative electrode tab satisfactory mechanical property of the invention, filming performance are good.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of negative electrode material characterized by comprising
MXene, the MXene are in stratiform, and are the main body of the negative electrode material；
Graphene, the graphene are inserted into the interlayer of the MXene with intercalated form.
2. negative electrode material according to claim 1, which is characterized in that the mass ratio of the MXene and the graphene is
1:0.1~0.8.
3. negative electrode material according to claim 1 or 2, which is characterized in that further include carbon nanotube, the carbon nanotube is passed through
It is through at the interlayer that the MXene and the graphene are formed；
Preferably, the MXene and the mass ratio of the carbon nanotube are 1:0.03~0.1.
4. a kind of negative electrode tab, which is characterized in that the negative electrode tab includes the described in any item negative electrode materials of claims 1 to 3.
5. negative electrode tab according to claim 4, which is characterized in that the negative electrode tab is described in any one of claims 1 to 3
The film layer that constitutes of negative electrode material, the quality accounting of the negative electrode material described in the film layer is 100%；
Preferably, the film layer with a thickness of 5~25um.
6. a kind of battery component, which is characterized in that including negative electrode tab described in diaphragm and claim 5, the negative electrode tab attachment
In the diaphragm.
7. a kind of preparation method of negative electrode material, which is characterized in that comprising steps of
S1: at 0~30 DEG C, after graphene dispersing solution to be added to the dispersion liquid of MXene, ultrasound is carried out in an inert atmosphere, is obtained
Suspension；
S2: the solvent in the suspension is removed to get the negative electrode material is arrived.
8. preparation method according to claim 7, which is characterized in that in step sl, also add in the dispersion liquid of MXene
Carbon nanotubes dispersion liquid is entered；
Preferably, the mass ratio of the MXene, the graphene and the carbon nanotube are 1:0.1~0.8:0.03~0.1.
9. a kind of preparation method of negative electrode tab, which is characterized in that in the step S2 of claim 7 or 8, remove the suspension
In solvent, be that dry 3 under the conditions of 0~30 DEG C~for 24 hours, obtained film layer is taken off up to negative electrode tab after suction filtration.
10. a kind of preparation method of battery component, which is characterized in that
In the step S2 of claim 7 or 8, the solvent in the suspension is removed, is when filtering, suction filtration film is diaphragm, is taken out
After filter dry 3 under the conditions of 0~30 DEG C~for 24 hours to get arriving the battery component；Wherein,
The battery component includes diaphragm and the negative electrode tab for being attached to the diaphragm.
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