CN103198935A - Preparation method of graphene sheet modified spinel type lithium manganate or alpha type manganese dioxide electrode - Google Patents

Preparation method of graphene sheet modified spinel type lithium manganate or alpha type manganese dioxide electrode Download PDF

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CN103198935A
CN103198935A CN2013101365380A CN201310136538A CN103198935A CN 103198935 A CN103198935 A CN 103198935A CN 2013101365380 A CN2013101365380 A CN 2013101365380A CN 201310136538 A CN201310136538 A CN 201310136538A CN 103198935 A CN103198935 A CN 103198935A
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graphene film
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CN103198935B (en
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马厚义
江荣岩
崔聪颖
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Shandong University
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Abstract

The invention relates to a preparation method of a graphene sheet modified spinel type lithium manganate or an alpha type manganese dioxide electrode. The method comprises the following steps of: weighing a manganese-containing electrode material, a conductive agent and PVDF (polyvinylidene fluoride) binder powder in a mass ratio being 80:15:5, wherein the conductive agent is a graphene sheet or a mixture of the graphene sheet and an acetylene black conductive agent; preparing each raw material into slurry; and applying the slurry on an aluminum foil current collector and a nickel mesh current collector, and rolling. The preparation process is easy, the conductivity of the prepared electrode can be remarkably improved, and the velocity performance can be remarkably improved.

Description

The preparation method of a kind of graphene film modified spinelle type LiMn2O4 or α type manganese dioxide electrode
Technical field
The present invention relates to a kind of improvement LiMn 2O 4And α-MnO 2The method of rate capability is applied in anode material for lithium-ion batteries LiMn with graphene film as conductive additive 2O 4With electrochemical capacitor material α-MnO 2In the electrode, improve above-mentioned material conductivity and rate capability, belong to lithium ion battery and electrochemical capacitor additive technology field.
Background technology
In recent years, along with the continuous consumption of fossil energy and the environmental pollution that brings thereof are serious day by day, research and development effectively, the new forms of energy of environmental protection become the epoch problem of All Around The World.Under the background that the dependence to traditional energy is not broken away from as yet, the new energy is not used widely as yet, it is more and more important that energy storage becomes.How will have that the energy stores effectively now and in needs, discharge to satisfy the daily life demand fast, become a focus that obtains extensive concern.Lithium ion battery and electrochemical capacitor are because energy density height, power density height separately obtained a large amount of concerns and application in the energy storage system.Yet its main electrode material that adopts is (as LiCoO 2And RuO 2) because the effects limit of aspects such as cost, environmental protection is difficult in the big capacity energy storage system widely-used.Spinel-type LiMn 2O 4With α type MnO 2Then have advantages such as capacity height, cost be low, nontoxic, become the candidate material of anode material for lithium-ion batteries and electrochemical capacitor electrode material.Yet all there is the low shortcoming of electronic conductivity in two kinds of materials, have caused its charge transfer process under big current conditions slower, and specific capacity is lower, and rate capability is relatively poor.
Two kinds of materials are carried out the modification of conductivity, become the main flow approach at present.Common way is that some better conductivity materials such as material with carbon element (comprising mesoporous carbon (mesoporous carbon), carbon nano-tube (CNTs), Graphene (graphene) etc.), conducting metal etc. are prepared composite material with above-mentioned material.The conductivity of synthetic composite material is more much better than pure electrode material, thereby has improved the low weakness of its electronic conductivity, has improved its rate capability.Yet, this method complexity, wayward, and be difficult to realize suitability for industrialized production.
Summary of the invention
The objective of the invention is to overcome above-mentioned deficiency, and the preparation method of a kind of graphene film modified spinelle type LiMn2O4 or α type manganese dioxide electrode is provided, improve two kinds of conductivity of electrolyte materials and rate capability.
The present invention is achieved by the following technical solutions:
The preparation method of a kind of graphene film modified spinelle type LiMn2O4 or α type manganese dioxide electrode, step is as follows:
(1) take by weighing manganese electrode material, conductive agent and Kynoar (PVDF) adhesive powder by mass ratio 80:15:5, the manganese electrode material is LiMn 2O 4Or α-MnO 2, conductive agent is the mixture of graphene film or graphene film and acetylene black conductive agent, and the PVDF adhesive powder is dissolved in an amount of N-methyl pyrrolidone (NMP), forming mass fraction is the uniform solution of 0.77wt%～0.94wt%;
(2) place absolute ethyl alcohol to form slurries manganese electrode material and conductive agent, stir and to vapor away fully until ethanol, the mixed-powder that obtains is moved in the solution that step (1) obtains, continue to stir 0.5-1 hour to forming uniform slurries;
(3) slurries that step (2) is obtained are coated on aluminum foil current collector or the nickel screen collector, and above-mentioned collector is pressed with roll squeezer in dry back, and electrode material can closely be attached on the collector, obtains LiMn 2O 4Or α-MnO 2The modified electrode of material.
α-the MnO that obtains 2The modified electrode of material can directly use, LiMn 2O 4Electrode then needs to be assembled in the button cell (CR2032) and goes, and its rate capability is realized by the test to button cell.
Both preferred 1-2:1 of mass ratio in the mixture of the described graphene film of above-mentioned steps (1) and acetylene black conductive agent.
Coating thickness is 150 ± 10 μ m on the described aluminum foil current collector of step (3), and (nickel screen is cut into 1cm * 2cm size, and the nickel screen specification of use is 60 orders), the area of filming are 0.5 ± 0.1cm on the nickel screen collector 2(be that the active material area that is coated with on each nickel screen is about 0.5cm 2, the back nickel screen of filming is covered by the black active material fully).
Preferably be coated with in aluminum foil current collector in the step (3) and contain LiMn 2O 4Slurries, be coated with at the nickel screen collector and contain α-MnO 2Slurries.
For better distinguish material of the present invention and unmodified material, according to the different quality mark of graphene film in the total material of each electrode, respectively electrode is labeled as not graphitiferous alkene sheet of LMO() and LMO-G(5wt%, 10wt% and 15wt%) and α-MnO 2(not graphitiferous alkene sheet) and α-MnO 2-G(5wt%, 10wt% and 15wt%).
Because graphene film is a kind of high conductivity material with carbon element with layer structure, so they can be by " face-point " conduction mode in conjunction with many LiMn in electrode 2O 4And α-MnO 2Material granule (as Fig. 3).And therefore the acetylene black conductive agent can only pass through " point-point " conduction mode in conjunction with above-mentioned electrode material granules owing to be particulate material.Clearly, " face-point " conduction mode is a kind of more effective conduction mode, and therefore the conductivity of above-mentioned electrode can be improved significantly.The stability of the long circulation time of electrode material experience is also improved significantly by suitable amount of graphite alkene additive.
It should be noted that therefore graphene film can not always have the partial electrode material and be caused its performance to be difficult to obtain performance by the conductive agent connection in conjunction with each electrode material granules.And when having the acetylene black conductive agent to exist in the electrode, this part material can be by the combination of acetylene black particle.In addition, because the particle of acetylene black conductive agent is can be filled in the space of graphene film and electrode material to combine with them, produces " fillings " effect (as Fig. 3), so understand conductive network of existence in the entire electrode.Rely on the cooperative effect of " face-point " conduction mode and " filling " pattern, the conductivity of electrode is further enhanced.Therefore the rate capability of electrode material is significantly improved.
The consumption of the realization of above-mentioned cooperative effect and Graphene additive has direct relation.When Graphene is very few, " face-point " conduction mode in the electrode a little less than; When Graphene was excessive, on the one hand, because the Graphene planar structure, its Van der Waals force was bigger, so Graphene sector-meeting generation clustering phenomena, and the efficient reduction in conjunction with electrode material makes that " face-point " conduction mode dies down; On the other hand, when not having the acetylene black conductive agent to exist in the electrode, the synergy of " filling " pattern and two kinds of patterns has not existed, the conductivity meeting variation of electrode, so LMO-G(15wt%) electrode capacity under high magnification is almost 0, and α-MnO 2-G(15wt%) the ratio electric capacity of electrode is not seen than α-MnO yet 2What exceed.
Compared with prior art, the present invention has the following advantages:
1. the not LMO of graphitiferous alkene sheet and α-MnO 2The test result of electrode can contrast according to its result in Fig. 1 and Fig. 2, finds out that the stability of the long circulation time of experience is improved significantly by suitable amount of graphite alkene additive.
As long as the graphene film of good dispersion is added in the electrode material in the certain mass ratio, because its distinctive planar structure and high conductivity, the conductivity of entire electrode can be improved significantly, and rate capability also can improve.
2. simple to operate, whole process does not have complicated technology, is convenient to realize industrial applications, and the preparation technology of grapheme material is comparatively easy, can satisfy the large-scale production needs.
Description of drawings
Fig. 1 is the rate capability performance of Different L MO-G electrode, a: under the various multiplying powers of 0.5-10C; Under the b:20C multiplying power.
Fig. 2 is different α-MnO 2The rate capability performance of electrode;
Fig. 3 is the conduction schematic diagram that contains the electrode of graphene conductive additive.
Embodiment
Further specify below in conjunction with embodiment.
Embodiment 1
(1) takes by weighing LiMn by mass ratio 80:15:5 2O 4Material, conductive agent and PVDF adhesive powder, conductive agent are graphene film, and the PVDF adhesive powder is dissolved in an amount of N-methyl pyrrolidone (NMP);
(2) with LiMn 2O 4Material and conductive agent place absolute ethyl alcohol to form slurries, stirring vapors away fully until ethanol, material reverted to Powdered again and mixed this moment, and the mixed-powder that obtains is moved in the solution that step (1) obtains, and continued to stir 0.5 hour to forming uniform slurries;
(3) slurries that step (2) is obtained are coated in (coating thickness is approximately 150 μ m) on the aluminum foil current collector, and above-mentioned collector is pressed with roll squeezer in dry back, and electrode material can closely be attached on the collector, gets LMO-G(15wt%) electrode.
Embodiment 2
Step is with embodiment 1, and difference is that the conductive agent that uses is the mixture of graphene film and acetylene black, and the quality proportioning is 10:5, gets LMO-G(10wt%) electrode.
Embodiment 3
Step is with embodiment 1, and difference is that the conductive agent that uses is the mixture of graphene film and acetylene black, and the quality proportioning is 5:10, gets LMO-G(5wt%) electrode.
Embodiment 4
(1) takes by weighing α-MnO by mass ratio 80:15:5 2Material, conductive agent and PVDF adhesive powder, conductive agent are graphene film, and the PVDF adhesive powder is dissolved in an amount of N-methyl pyrrolidone (NMP);
(2) with α-MnO 2Material and conductive agent place absolute ethyl alcohol to form slurries, stirring vapors away fully until ethanol, material reverted to Powdered again and mixed this moment, and the mixed-powder that obtains is moved in the solution that step (1) obtains, and continued to stir 0.5 hour to forming uniform slurries;
(3) slurries that step (2) is obtained are coated on the nickel screen collector, and nickel screen is cut into 1cm * 2cm size, and the nickel screen specification of use is 60 orders, and the area of filming is 0.5 ± 0.1cm 2(be that the active material area that is coated with on each nickel screen is about 0.5cm 2, the back nickel screen of filming is covered by the black active material fully), above-mentioned collector is pressed with roll squeezer in dry back, and electrode material can closely be attached on the collector, gets α-MnO 2-G(15wt%) electrode.
Embodiment 5
Step is with embodiment 4, and difference is that the conductive agent that uses is the mixture of graphene film and acetylene black, and the quality proportioning is 10:5, gets α-MnO 2-G(10wt%) electrode.
Embodiment 6
Step is with embodiment 4, and difference is that the conductive agent that uses is the mixture of graphene film and acetylene black, and the quality proportioning is 5:10, gets α-MnO 2-G(5wt%) electrode.
Performance test
Tested respectively among the present invention that the Graphene mass fraction is the rate capability of each electrode under 5wt%, 10wt% and three kinds of situations of 15wt% in the electrode, graphene film is by using hydrazine hydrate (N 2H 4H 2O) (Graphene Oxide, method GO) makes redox graphene.GO is then by adopting improved Hummers method by graphite powder preparation [Q.Cheng, J.Tang, J.Ma, H.Zhang, N.Shinya, L.C.Qin, Graphene and nanostructured MnO 2Composite electrodes for supercapacitors.Carbon, 2011,49,2917-2925].
The preparation process of graphene film is:
(1) takes by weighing 0.05g GO powder, it is joined in the 60mL ultra-pure water, then it is carried out ultrasonic processing 2h, make the GO powder to be distributed to equably in the ultra-pure water, form the GO dispersion liquid.
(2) in above-mentioned dispersion liquid, drip NH 3H 2O uses magnetic stirring apparatus that it is stirred simultaneously, and the pH value of regulating this dispersion liquid approximates 10, continues to stir 0.5h.
(3) under constantly stirring, in dispersion liquid, slowly be added dropwise to 250 μ L N 2H 4H 2O(85wt%), then dispersion liquid is placed in the water-bath, setting heating-up temperature is 90 ° of C, it is carried out agitating heating 15h after, stop heating, treat that it cools off naturally, obtains the aqueous dispersions of graphene film.
(4) use centrifuge, the grapheme material that obtains is separated from liquid, and respectively cleaned three times with ultra-pure water and absolute ethyl alcohol, be placed on 80 ° of dry 12h of C in the drying box then.
The different electrodes that will contain above-described embodiment preparation are designated as LMO-G(5wt%, 10wt%, 15wt% respectively) and α-MnO 2-G(5wt%, 10wt%, 15wt%).
(1) rate capability of various electrodes is tested
The rate capability of LMO and various LMO-G electrodes carries out constant current charge-discharge by the button cell (CR2032) to its assembling to be tested to realize, being assembled in the glove box of battery carried out, LMO and LMO-G electrode are as anode, lithium sheet (purity is more than 99.9%) is as battery cathode, 1mol L -1LiPF 6Solution [solvent is that volume ratio is the ethylene carbonate(EC of 1:1) and dimethyl carbonate(DMC)] be electrolyte.Charge-discharge test uses Land charge-discharge test instrument to realize that discharging and recharging potential region is 3.5-4.3V(vs.Li/Li +), charge-discharge magnification is respectively 0.5,2,5,10 and 20C(1C=148mA g -1).α-MnO 2With various α-MnO 2The rate capability of-G electrode is tested to carry out by its three-electrode system as work electrode is carried out constant current charge-discharge, and (1 * 2cm) as to electrode, and saturated calomel electrode (SCE) is as reference electrode, 0.5mol L for the Pt sheet -1Na 2SO 4The aqueous solution is as electrolyte.Charge-discharge test uses the CHI760C electrochemical workstation to realize, discharge and recharge potential region to be-0.2-0.8V(vs.SCE), charging and discharging currents density is 1000mA g -1
(2) rate capability of various electrodes performance
When containing suitable amount of graphite alkene conductive additive, the rate capability of two kinds of materials has had tangible lifting.With LiMn 2O 4, be example (as shown in Figure 1), LMO-G(5wt%) specific discharge capacity of electrode under the various multiplying powers of 0.5-20C all is higher than the LMO electrode far away.Especially under 10C and the big multiplying power of 20C, LMO-G(5wt%) the initial discharge specific capacity of electrode is respectively 88 and 78mAh g -1, be higher than 70 and 60mAh g of LMO electrode far away -1Again with α-MnO 2Material is example (as Fig. 2), α-MnO 2-G(10wt%) electrode is at 1000mA g -1Through 1000 charge and discharge cycles, its discharge maintains 80F g all the time than electric capacity under the current density -1More than, be better than α-MnO far away 2Electrode.The stability of these two kinds of long circulation times of material experience is also improved significantly by suitable amount of graphite alkene additive.
The rate capability of two kinds of materials is obviously improved, and is caused by above-mentioned " graphene film ' face-point ' conduction mode is with the synergy of ' filling ' mode producing of AB particle ".At first, graphene film is by the higher face-point of electrical efficiency " conduction mode improved the conductivity of electrode; Secondly, the AB particle relies on its " filling " pattern, has connected those not by the isolated electrode material granules of graphene film combination, makes that the material in the entire electrode combines, and forms an effective conductive network, has further improved the conductivity of electrode.Given this, the rate capability of two kinds of materials be improved significantly.

Claims (4)

1. the preparation method of a graphene film modified spinelle type LiMn2O4 or α type manganese dioxide electrode is characterized in that, comprises that step is as follows:
(1) take by weighing manganese electrode material, conductive agent and Kynoar PVDF adhesive powder by mass ratio 80:15:5, the manganese electrode material is LiMn 2O 4Or α-MnO 2, conductive agent is the mixture of graphene film or graphene film and acetylene black conductive agent, and the PVDF adhesive powder is dissolved in an amount of N-methyl pyrrolidone, forming mass fraction is the uniform solution of 0.77wt%～0.94wt%;
(2) place absolute ethyl alcohol to form slurries manganese electrode material and conductive agent, stir and to vapor away fully until ethanol, the mixed-powder that obtains is moved in the solution that step (1) obtains, continue to stir 0.5-1 hour to forming uniform slurries;
(3) slurries that step (2) is obtained are coated on aluminum foil current collector or the nickel screen collector, and above-mentioned collector is pressed with roll squeezer in dry back, and electrode material can closely be attached on the collector, obtains LiMn 2O 4Or α-MnO 2The modified electrode of material.
2. the preparation method of a kind of graphene film modified spinelle type LiMn2O4 according to claim 1 or α type manganese dioxide electrode is characterized in that both mass ratioes select 1-2:1 in the mixture of the described graphene film of step (1) and acetylene black conductive agent.
3. the preparation method of a kind of graphene film modified spinelle type LiMn2O4 according to claim 1 or α type manganese dioxide electrode, it is characterized in that, coating thickness is 150 ± 10 μ m on the described aluminum foil current collector of step (3), on the nickel screen collector, nickel screen is cut into 1cm * 2cm size, and the area of filming is 0.5 ± 0.1cm 2
4. the preparation method of a kind of graphene film modified spinelle type LiMn2O4 according to claim 1 or α type manganese dioxide electrode is characterized in that, is coated with in aluminum foil current collector in the step (3) to contain LiMn 2O 4Slurries, be coated with at the nickel screen collector and contain α-MnO 2Slurries.
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WO2016005590A1 (en) * 2014-07-10 2016-01-14 Repsol, S.A. Cathode for lithium batteries
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CN110474099A (en) * 2019-07-12 2019-11-19 大连恒超锂业科技有限公司 A kind of preparation method of lithium ion battery anode glue size
CN118117097A (en) * 2024-03-06 2024-05-31 超威电源集团有限公司 Stainless steel current collector with protective coating and preparation method and application thereof

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