CN104300129A - Battery, battery cathode, battery cathode material and preparation method thereof - Google Patents
Battery, battery cathode, battery cathode material and preparation method thereof Download PDFInfo
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
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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 invention relates to a battery cathode material and a preparation method thereof. The cathode material at least comprises the active material elemental silicon and reduced graphene oxide, and also includes polyaniline. Also, the elemental silicon has the double cladding layer of polyaniline and reduced graphene oxide. On the one hand, the special internal structure of polyaniline can well inhibit huge volume change of silicon particles in a charge-discharge process, thus improving the cycle performance of the battery; and on the other hand, both polyaniline and graphene have excellent electrical conductivity, and can significantly improve the charge-discharge capacity of the material. The invention also relates to a battery cathode and a battery containing the cathode material. The battery cathode and the battery provided by the invention have high charge-discharge capacity and good cycle performance, thus being suitable for various mobile electronic equipment.
Description
Technical field
The present invention relates to energy storage material technical field, more particularly, relate to negative material of a kind of battery and preparation method thereof and the battery cathode containing this negative material and the battery assembled by this negative pole.
Background technology
Lithium ion battery is as a kind of high energy density cells of the prior art, large quantifier elimination has been carried out by industry personnel, the advantage such as it has that quality is light, volume is little, discharge voltage is high, have extended cycle life, memory-less effect, self discharge are little, has been widely used in the portable electric appts such as mobile phone, digital camera, notebook computer.But current lithium ion battery also exists many technical bottlenecks, as poor in the charge-discharge performance under large multiplying power, energy density is not high enough, security performance is low, therefore can't realize the scale Application and Development of large-scale lithium ion battery as batteries of electric automobile.What commercial Li-ion battery negative material generally adopted is graphite-like material with carbon element, but its theoretical specific capacity only has 372mAh/g, thus limit the further raising of lithium ion battery specific energy, growing high-energy, the demand of high-capacity battery can not be met.Therefore, researcher is devoted to develop and has more high power capacity and safe and reliable Novel anode material carrys out alternative graphite-like Carbon anode.
In recent years, can attract wide attention with the negative material of the silicon of lithium generation alloying reaction as lithium ion battery.The theoretical capacity of silicon, up to 4200mAh/g, uses silicon significantly can improve the energy density of lithium ion battery as negative pole.But the usual cycle performance of silicon based anode material is poor, this is because in the process of de-/embedding lithium ion, it exists huge change in volume, causes silicon grain fragmentation, efflorescence, changes silicon electrode pattern, thus makes material lose conduction connection.In addition, silicon belongs to semi-conducting material, and its intrinsic conductivity only has 6.7 × 10
-4s/cm, high rate during charging-discharging is poor.The method improving silicon materials performance mainly contains that carbon is coated at present, particle nanometer, prepare silicon alloy, prepare silicon thin film etc.
Chinese patent CN102420323A discloses a kind of lithium ion battery silicon/graphene/carbon composite negative pole material, and wherein Graphene and carbon are distributed between silicon grain surface and silicon grain.Because Graphene and carbon all have good electron conduction, therefore the conductivity of composite material improves two orders of magnitude compared with elemental silicon, thus improves the specific capacity of composite material, and under 100mA/g, first discharge specific capacity is 1400mAh/g.In charge and discharge process, although the change in volume of silicon have also been obtained suppression to a certain degree, the cycle performance of composite material is still not ideal enough, circulate after 200 times, capacity attenuation nearly 50%.
Summary of the invention
The object of the present invention is to provide a kind of silicon based composite material and preparation method thereof, to suppress the change in volume of silicium cathode material in charge and discharge process, improve its conductivity, thus improve cycle performance and the high rate performance of battery.
The invention provides a kind of cell negative electrode material, at least comprise active material elemental silicon and redox graphene, described negative material also comprises polyaniline.
Preferably, the mass ratio of described active material elemental silicon, polyaniline and redox graphene is K1:K2:K3, and wherein K1 is 55 ~ 81, K2 be 18 ~ 28, K3 is 7 ~ 11.
Preferably, described active material elemental silicon comprises nano level spheric granules.
Preferably, the active material elemental silicon in described negative material has two-layer coating layer, and ground floor is polyaniline, and the second layer is redox graphene.
Present invention also offers a kind of battery cathode, described battery cathode comprises negative material as above.
Present invention also offers a kind of battery, comprise positive pole, negative pole, electrolyte and barrier film, described negative pole comprises negative material as above.
Present invention also offers a kind of preparation method of cell negative electrode material, described preparation method comprises the steps:
Add elemental silicon particle and surfactant in deionized water, carry out ultrasonic disperse; In-situ polymerization prepares the mixture of polyaniline-coated silicon grain; Prepare redox graphene solution; Redox graphene solution is added in the mixture of polyaniline-coated silicon grain; Filter, wash and the dry mixture processing silicon, polyaniline and redox graphene.
Preferably, described elemental silicon comprises nano level spheric granules.
Preferably, described surfactant comprises DTAB and n-butanol.
Preferably, the mixture preparing described polyaniline-coated silicon grain comprises the steps:
Aniline monomer and Bronsted acid is added in elemental silicon dispersion liquid;
Ice bath adds the aqueous solution of oxidant ammonium persulfate under stirring, in-situ polymerization generates the mixture of polyaniline-coated silicon grain.
Preferably, described Bronsted acid comprises one or more in hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, oxalic acid, citric acid, tartaric acid, p-methyl benzenesulfonic acid, camphorsulfonic acid, sulfosalicylic acid, dodecyl sodium sulfonate, DBSA, naphthalene sulfonic acids, dinonylnaphthalene sulfonic acid, polystyrolsulfon acid, polyvinyl sulfonic acid, sulfamic acid and aminobenzenesulfonic acid.
Preferably, the mode of described filtration comprises vacuum filtration or centrifugal filtration.
Preferably, described washing carries out successively with ethanol, water and hydrochloric acid.
Preferably, described drying process carries out under vacuum, and the temperature range of described drying process is 65-75 DEG C, and the time range of dry process is 10-14 hour.
Compared with prior art, beneficial effect of the present invention:
The present invention utilizes home position polymerization reaction, and prepared a kind of negative material of battery, described negative material comprises active material elemental silicon, redox graphene and polyaniline, and silicon has two-coat, and ground floor is polyaniline, and the second layer is redox graphene.
Redox graphene has excellent electron conduction, can separate silicon grain simultaneously, silicon grain is disperseed better, reduces and reunites.Therefore, redox graphene be coated on silicon grain surface or be dispersed between silicon grain, the electron conduction of silicon materials can be significantly improved, increasing the charge/discharge capacity of silicon based composite material.
Polyaniline is a kind of conducting polymer of ambient stable, its have excellent conductivity, various structures, to features such as the good stability of oxygen and water and reversible doping/dedopings.By polyaniline in-stiu coating silicon grain, one deck conductive coating can be formed on silicon grain surface on the one hand, improve the conductivity of silicon; Polyaniline has special " nido " structure on the other hand, the polyaniline-coated layer on silicon grain surface and be dispersed in intergranular polyaniline matrix and silicon grain can be embedded in its " nest ", this " nido " structure can cushion the enormousness change of silicon grain in charge and discharge cycles process well, thus improves the cyclical stability of silicon materials widely.In addition, polyaniline has certain electro-chemical activity, and therefore to a certain extent, it can also increase the charge/discharge capacity of electrode material; Polyaniline also has excellent heat conductivility, can improve the thermal stability of battery.
Negative material provided by the invention, on the basis of silicon and redox graphene compound, further interpolation polyaniline, first by polyaniline in-stiu coating at elemental silicon particle surface, and then coated one deck redox graphene, well can not only suppress the change in volume of silicon like this, also can improve its conductivity.Compared with elemental silicon, the discharge capacity of silicon based composite material, cycle performance and high rate performance are obtained for obvious improvement, and under 200mA/g, circulate after 15 times, the specific capacity of silicon based composite material is about 2 times of elemental silicon.
Accompanying drawing explanation
Below in conjunction with drawings and embodiments, the invention will be further described.
Fig. 1 is the transmission electron microscope picture (TEM) of the n-Si/PANi/RGO negative material that embodiment 1 provides;
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of the n-Si/PANi/RGO negative material that embodiment 1 provides;
Fig. 3 is that the discharge capacity of the battery that embodiment 1 provides and coulombic efficiency are to the graph of a relation of cycle-index;
Fig. 4 is the charge/discharge capacity of the battery that embodiment 1 provides and the graph of a relation of voltage;
Fig. 5 is the energy spectrum analysis figure (EDS) of the n-Si/PANi/RGO negative material that embodiment 1 provides
Fig. 6 is the TEM figure of the n-Si/PANi material that comparative example 1 provides;
Fig. 7 is the SEM figure of the n-Si/PANi material that comparative example 1 provides;
Fig. 8 is that the discharge capacity of the battery that comparative example 1 provides and coulombic efficiency are to the graph of a relation of cycle-index;
Fig. 9 is the charge/discharge capacity of the battery that comparative example 1 provides and the graph of a relation of voltage;
Figure 10 is the TEM figure of the n-Si material that comparative example 2 provides;
Figure 11 is the SEM figure of the n-Si material that comparative example 2 provides;
Figure 12 is that the discharge capacity of the battery that comparative example 2 provides and coulombic efficiency are to the graph of a relation of cycle-index;
Figure 13 is the charge/discharge capacity of the battery that comparative example 2 provides and the graph of a relation of voltage;
The negative material that Figure 14 is embodiment 1, comparative example 1 and comparative example 2 provide thermogravimetric analysis figure (TGA);
The high rate performance of the battery that Figure 15 is embodiment 1, comparative example 1 and comparative example 2 provide is to the relation comparison diagram of cycle-index.
Embodiment
The embodiment of the invention discloses a kind of negative material of battery, at least comprise active material elemental silicon (Si), redox graphene (RGO), also comprise polyaniline (PANi).
Active material elemental silicon is preferably nanoscalar silicon particles (n-Si), and pattern is spherical or almost spherical, can purchase from the market.
Strictly speaking, Graphene is a kind of material of the individual layer laminated structure be made up of carbon atom, and wherein, carbon atom forms honeycomb lattice structure, and Graphene has the high electron mobility being about 20000-50000cm/Vs, and conductivity is up to 10
6s/cm is the material that the electric conductivity of current mankind discovery is the highest.If it to be added to the electrode material compound of battery, the electronic conductivity of electrode material can be improved, thus improve the charge-discharge performance of material under large multiplying power.The synthetic method of Graphene mainly contains two kinds: mechanical means and chemical method.Mechanical means comprises the method for micromechanics partition method, epitaxy method and heating SiC; Chemical method is chemical reduction method and chemical cleavage method.
Redox graphene (RGO) in the present invention is proper Graphene not, and in the structure of RGO, the carbon atom number of plies can be multilayer, and can with other functional group (as fluorine, nitrogen, oxygen, carbonyl, carboxyl, hydroxyl etc.).By by graphite oxidation, form graphene oxide, then this graphene oxide is reduced, prepare redox graphene (RGO) thus.Although the conductivity of RGO is slightly inferior to Graphene, other functional group residual on RGO is conducive to it on the contrary and disperses in other matrix or combine, and prepares various composite material with this, and this RGO is easy to batch preparation.
Polyaniline not only can improve the conductivity of silicon, the more important thing is that it has special " nido " structure, by itself and elemental silicon compound, silicon can be made to be embedded in " nest " of polyaniline, this just can suppress the enormousness change of silicon in charge and discharge process well, improves the cycle performance of silicon materials.
Negative material elemental silicon/RGO/PANi in the present invention is also preferably nanoscale, and pattern is spherical or class is spherical, and wherein, the mass ratio of silicon, polyaniline and redox graphene is 55 ~ 81:18 ~ 28:7 ~ 11.Active material elemental silicon has two-layer coating layer, and ground floor is polyaniline, and the second layer is redox graphene, and polyaniline and redox graphene are also distributed between negative material particle.PANi matrix in the PANi coating layer on silicon grain surface and compound can suppress the change in volume of silicon grain in charge and discharge process; On the other hand, PANi also can improve the conductivity of compound.Particle can be separated into different sheets by the RGO sheet in compound, and silicon grain so just can be made to disperse better, reduces the reunion of silicon grain; And RGO has high conductivity, this also can improve the conductivity of compound.Therefore, the conductivity of composite material and cyclicity can be greatly improved compared to elemental silicon.
Present invention further teaches a kind of battery cathode, comprise negative material as above.
Present invention further teaches a kind of battery, comprise positive pole, negative pole, electrolyte and barrier film, negative pole comprises negative material as above.
Positive pole comprise can reversible deviate from-material of embedded ion or sulfenyl material.Concrete, positive electrode can adopt can the reversible material deviating from-embed lithium ion, sodium ion, zinc ion or magnesium ion.Positive electrode active materials also can adopt sulfenyl material, and sulfenyl material is selected from elementary sulfur, Li
2s
n, containing sulfur compound, organic sulfur compound or carbon-sulfur polymer (C
2s
v)
min at least one, wherein, n>=1,2.5≤v≤50, m>=2.
Electrolyte can be liquid state, gel state or solid-state.When electrolyte is liquid, barrier film is preferably the macromolecule membrane of porous, as microporous polypropylene film etc.; Electrolyte be gel state or solid-state time, battery formation on can use barrier film.
In order to ensure in charge and discharge process, between the positive pole of battery and negative pole, there is the metal ion of deviating from-embedding, when the sulfur-based positive electrode material selected and silicon based anode material be not simultaneously containing this metal ion, pre-embedding ion processing be carried out to positive pole and/or negative pole.Concrete pre-embedding ionic means is not limit, and comprises chemical reaction or electrochemical reaction method etc.
Present invention further teaches a kind of preparation method of cell negative electrode material, negative material comprises active material elemental silicon (Si), redox graphene (RGO), also comprises polyaniline (PANi).
Concrete, the silicon based composite material that preparation method mainly adopts situ aggregation method to cover to produce polyaniline and redox graphene double-contracting.In-situ polymerization is that one all adds reactive monomer (or its solubility performed polymer) and catalyst in decentralized photo (or continuous phase), and core material is decentralized photo.Because monomer (or performed polymer) is solvable in single-phase, and its polymer is insoluble in whole system, so polymerization reaction occurs on decentralized photo core.Reaction starts, monomer pre-polymerization, and performed polymer is polymerized, and after performed polymer aggregate size progressively increases, is deposited on the surface of core material.In the present invention, core material is elemental silicon, and monomer is aniline, after in-situ polymerization, forms polyaniline-coated layer on silicon grain surface, and then with the composite material of the coated polyaniline of redox graphene and silicon, finally obtains silicon/RGO/PANi negative material.
A preparation method for cell negative electrode material, preparation method comprises the steps:
Add elemental silicon particle and surfactant in deionized water, carry out ultrasonic disperse; In-situ polymerization prepares the mixture of polyaniline-coated silicon grain; Prepare redox graphene solution; Redox graphene solution is added in the mixture of polyaniline-coated silicon grain; Filter, wash and the dry mixture processing silicon, polyaniline and redox graphene.
Prepared the silicon based composite material of polyaniline-coated by home position polymerization reaction, first need to prepare silicon decentralized photo, be scattered in deionized water by elemental silicon, elemental silicon is preferred nano level spheric granules also; But due to the dispersiveness of silicon in water good not, so need to add surfactant make it disperse evenly, stir with ultrasonic simultaneously, form uniform silicon dispersion liquid.Concrete, surfactant is preferably DTAB (DTBA) and n-butanol.
Then in elemental silicon dispersion liquid, add aniline monomer and ammonium persulfate, it is coated to carry out in-situ polymerization.The mixture (Si/PANi) preparing polyaniline-coated silicon grain comprises the steps: to add aniline monomer and Bronsted acid in elemental silicon dispersion liquid; Ice bath adds the aqueous solution of oxidant ammonium persulfate under stirring, in-situ polymerization generates the mixture of polyaniline-coated silicon grain.Because aniline is insoluble in water, will carry out polymerization at aqueous phase must by water acidifying, namely with Bronsted acid, aniline is protonated, greatly can not only increase the solubility of aniline in water like this, and makes polyaniline have conductivity due to the doping of Bronsted acid.Simultaneously, ammonium persulfate serves as the effect of oxidant in system, concrete effect is that catalytic oxidation aniline generates nitrenium thus causes chain to cause and chain growth, ammonium persulfate is more stable in acid condition, and more easily decompose under alkali condition and produce oxygen and ozone, or oxidize water Hydrogen Peroxide and ammonium hydrogen sulfate.
Concrete, Bronsted acid comprises one or more in hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, oxalic acid, citric acid, tartaric acid, p-methyl benzenesulfonic acid, camphorsulfonic acid, sulfosalicylic acid, dodecyl sodium sulfonate, DBSA, naphthalene sulfonic acids, dinonylnaphthalene sulfonic acid, polystyrolsulfon acid, polyvinyl sulfonic acid, sulfamic acid and aminobenzenesulfonic acid.
The above-mentioned mixture (Si/PANi) redox graphene (RGO) preparing the polyaniline-coated silicon of gained is carried out secondary coated, namely redox graphene solution is first prepared, again redox graphene solution is added in the mixture of polyaniline-coated silicon grain, because obtained RGO itself is electronegative, and in Si/PANi mixture, there is positively charged DTAB, electrostatic force can be there is between both, therefore RGO can be compound to the surface of Si/PANi well, form silicon, the mixture (Si/PANi/RGO) of polyaniline and redox graphene, finally it is filtered, washing and dry process, final acquisition Si/RGO/PANi negative material.
Concrete, the mode of filtration can adopt vacuum filtration or centrifugal filtration; Wash available ethanol, water and hydrochloric acid and successively several washing is carried out to the mixture of silicon, polyaniline and redox graphene; Dry process can be carry out under vacuum, and the temperature range of dry process is 65-75 DEG C, and the time range of dry process is 10-14 hour.
The preparation of redox graphene solution comprises the steps: to prepare graphene oxide solution, then reduces described graphene oxide solution, obtains redox graphene solution.The spendable redox graphene of the present invention obtains by graphite linings being separated, and graphite can use native graphite or Delanium.First graphite oxidation is carried out ultrasonic stripping to prepare graphene oxide, method for oxidation can adopt Hummer method etc.Then reduce to graphene oxide, obtain redox graphene (RGO), method of reducing can adopt chemical reduction method, high temperature reduction method or electrochemical reducing etc.
The present invention preferably adopts following mode to test physical property and the chemical property of cell negative electrode material prepared by the present invention.
Test physical property
By using transmission electron microscope (TEM), to observe microscopic appearance and the grain diameter of negative material.
By using ESEM (SEM), to observe microscopic appearance and the grain diameter of negative material.
By thermogravimetric analysis (TGA), to observe the final each constituent content of negative material.
By energy spectrum analysis (EDS), to observe the final individual constituent content ratio of negative material.
Test chemical property
Electrode composite material, the conductive acetylene of battery the present invention prepared are black, sodium carboxymethylcellulose (CMC) is join in deionized water at 75: 10: 15 in mass ratio, after mixing, positive plate is made in oven dry, and in glove box, be assembled into 2025 button cells, wherein negative pole is lithium sheet, barrier film is Celgard2250, and electrolyte is for containing 1M lithium hexafluoro phosphate (LiPF
6) and the ethylene carbonate (EC) of vinylene carbonate (VC) additive of 2wt% and the mixed solution (EC/DEC mass ratio=1:1) of diethyl carbonate (DEC).
Be 200mA/g in current density, under voltage range is 0.01 ~ 2V, carry out constant current charge-discharge performance test.
The all specialties used in the present invention and scientific words and one skilled in the art the meaning be familiar with identical.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that better implementation method described in literary composition and material only present a demonstration.
Below in conjunction with embodiment, further illustrate content of the present invention.Should be appreciated that enforcement of the present invention is not limited to the following examples, any pro forma accommodation make the present invention and/or change all will fall into scope.In the present invention, if not refer in particular to, all percentage is unit of weight, and all equipment and raw material etc. all can be buied from market or the industry is conventional.
Embodiment 1
The preparation of n-Si/PANi/RGO
First in 100ml deionized water, add nano-silicon (n-Si) particle 0.3g, surfactant sodium dodecyl base trimethylammonium bromide (DTBA) 0.5g and n-butanol 0.375ml, ultrasonic disperse said mixture 30 minutes, obtains uniform brown suspension.
Then while stirring, in brown suspension, dropwise add the 30ml HCl(pH=1 containing 0.3ml (3.3mmol) aniline monomer) solution.Said mixture ice bath is stirred, slowly drips wherein simultaneously and dissolved 0.19g(0.825mmol) the 10ml deionized water of ammonium persulfate, it can make aniline monomer carry out in-situ polymerization as oxidant.This polymerization process continues 12 hours, the polyaniline of obtained green and brown secondary colour and nano-silicon mixture (n-Si/PANi) solution.
Get a reaction vessel, add 0.8g native graphite and the 23ml concentrated sulfuric acid, react 24 hours, then add 100mg sodium nitrate (NaNO wherein
3), stir after 5 minutes, above-mentioned reaction vessel is placed in less than 20 DEG C ice baths, and slowly add 3g potassium permanganate (KMnO
4).Be heated to 100 DEG C by after the dilution of above-mentioned suspension-turbid liquid, and maintain 15 minutes, then by this suspension-turbid liquid with 5% HCl and water washing, obtain brown uniform graphite oxide solution.The above-mentioned obtained graphite oxide of ultrasonic disperse 30 minutes, is then diluted with water to concentration 0.05wt%.Uniform for above-mentioned 100ml dispersion mixed with 100ml water, then add the hydrazine solution of 100 μ l and the ammoniacal liquor of 0.7ml wherein, the mass ratio of hydrazine and graphene oxide is at about 7:10.Under vigorous stirring, the oil bath 1 hour at 95 DEG C of above-mentioned dispersion, after having reduced, hydrazine unnecessary in dispersion is then thoroughly removed by the ammoniacal liquor dialysis to 0.5%.Like this under ammoniacal liquor exists, obtain redox graphene (RGO) sheet by redox graphene.
In said n-Si/PANi mixture solution, slowly drip the RGO of the 0.025wt% of 200ml, the color of suspension becomes black thereupon.
Finally, vacuum filtration is carried out to black suspension, and successively with ethanol, deionized water and 0.15mol/LHCl washing several, obtain solid particle.By solid particle at 60 DEG C dry 12 hours in a vacuum furnace, finally obtain bottle-green n-Si/PANi/RGO compound.
Fig. 1 and Fig. 2 is transmission electron microscope picture (TEM) and the scanning electron microscope (SEM) photograph (SEM) of n-Si/PANi/RGO negative material.From Fig. 1 and Fig. 2, we can clearly be seen that composite material n-Si/PANi/RGO has spherical or class spherical structure, and grain diameter is nanoscale.By the electrostatic force between electronegative RGO sheet and positively charged DTAB, RGO sheet is compound to the surface of n-Si/PANi.Simultaneously between spheric granules, there is polyaniline and redox graphene, and particle " bridge " has been connected together.
Fig. 5 is the energy spectrum analysis figure (EDS) of n-Si/PANi/RGO negative material.Can find out that from Fig. 5 peak and nitrogen element one of of silicon, oxygen, carbon is not peak clearly clearly, show in obtained n-Si/PANi/RGO negative material containing silicon, oxygen, carbon and nitrogen element.Drawn by energy spectrum analysis, in obtained n-Si/PANi/RGO negative material, the mass fraction of C, N, O, Si is respectively 24.24%, 3.55%, 8.01%, 64.2%.This shows that three kinds of materials are well compounded in together, and silicon is main component.
The preparation of battery
The electrode composite material n-Si/PANi/RGO of battery previous step prepared, conductive acetylene are black, sodium carboxymethylcellulose (CMC) is join in deionized water at 75: 10: 15 in mass ratio, after mixing, positive plate is made in oven dry, and in glove box, be assembled into 2025 button cells, wherein negative pole is lithium sheet, barrier film is Celgard2250, and electrolyte is for containing 1M lithium hexafluoro phosphate (LiPF
6) and the ethylene carbonate (EC) of vinylene carbonate (VC) additive of 2wt% and the mixed solution (EC/DEC mass ratio=1:1) of diethyl carbonate (DEC).
The chemical property of the electrode material of lithium ion battery prepared by the present embodiment as shown in Figure 3 and Figure 4.Fig. 3 be the discharge capacity of battery and coulombic efficiency to the relation curve of cycle-index, Fig. 4 is the charge/discharge capacity of battery and the graph of a relation of voltage.As can be seen from the figure, battery first discharge specific capacity and charge specific capacity are respectively about 3800mAh/g and 3100mAh/g, and battery charging and discharging circulates, charge specific capacity after 20 times still can reach 2800mAh/g, and capability retention is up to about 90%.
Comparative example 1
The preparation of n-Si/PANi
The step of preparation n-Si/PANi and the similar of preparation n-Si/PANi/RGO, also comprise the dispersion of silicon nanoparticle and the in-situ polymerization of aniline monomer.Then polyaniline and nano-silicon mixture (n-Si/PANi) solution of the green obtained and brown secondary colour are carried out vacuum filtration, equally also successively with ethanol, deionized water and 0.15mol/L HCl washing several, obtain solid particle.By this particle at 60 DEG C dry 12 hours in a vacuum furnace, finally obtain the n-Si/PANi compound of color between green and brown.
Fig. 6 and Fig. 7 is TEM figure and the SEM figure of n-Si/PANi material.Similar with n-Si/PANi/RGO, composite material n-Si/PANi also has spherical or class spherical structure, and grain diameter is about 100nm.Wherein aniline monomer in-situ polymerization is at Si particle surface; Some Si particles " bridge " have been connected together by some polyanilines simultaneously.
The preparation of battery
The electrode composite material n-Si/PANi of battery previous step prepared, conductive acetylene are black, sodium carboxymethylcellulose (CMC) is join in deionized water at 75: 10: 15 in mass ratio, after mixing, positive plate is made in oven dry, and in glove box, be assembled into 2025 button cells, wherein negative pole is lithium sheet, barrier film is Celgard2250, and electrolyte is for containing 1M lithium hexafluoro phosphate (LiPF
6) and the ethylene carbonate (EC) of vinylene carbonate (VC) additive of 2wt% and the mixed solution (EC/DEC mass ratio=1:1) of diethyl carbonate (DEC).
The performance of the electrode material of lithium ion battery prepared by this comparative example as shown in Figure 8 and Figure 9.Fig. 8 be the discharge capacity of battery and coulombic efficiency to the relation curve of cycle-index, Fig. 9 is the charge/discharge capacity of battery and the graph of a relation of voltage.As can be seen from the figure, battery first discharge specific capacity and charge specific capacity are respectively about 3000mAh/g and 2500mAh/g, and the battery charging and discharging charge specific capacity after 20 times that circulates is 1750mAh/g, and capability retention is about 70%.Can find out thus, battery in embodiment 1 has higher charging and discharging capacity and better cycle performance relative to the battery in comparative example 1, this result shows with the common modified silicon of RGO and PANi than the better effects if only using PANi modified silicon, also show that RGO can improve the conductivity of silicon materials simultaneously, increase its specific capacity, also can improve its cycle performance simultaneously.
Comparative example 2
Figure 10 and Figure 11 is TEM figure and the SEM figure of n-Si material.As can be seen from the figure n-Si has spherical structure, and particle diameter is at about 60nm.
The preparation of battery
Be join in deionized water at 75: 10: 15 in mass ratio by black to electrode material n-Si, conductive acetylene, sodium carboxymethylcellulose (CMC), after mixing, positive plate is made in oven dry, and in glove box, be assembled into 2025 button cells, wherein negative pole is lithium sheet, barrier film is Celgard2250, and electrolyte is for containing 1M lithium hexafluoro phosphate (LiPF
6) and the ethylene carbonate (EC) of vinylene carbonate (VC) additive of 2wt% and the mixed solution (EC/DEC mass ratio=1:1) of diethyl carbonate (DEC).
The performance of the electrode material of lithium ion battery prepared by this comparative example as shown in Figure 12 and Figure 13.Figure 12 be the discharge capacity of battery and coulombic efficiency to the relation curve of cycle-index, Figure 13 is the charge/discharge capacity of battery and the graph of a relation of voltage.As can be seen from the figure, battery first discharge specific capacity and charge specific capacity are respectively about 3600mAh/g and 3200mAh/g, and the battery charging and discharging charge specific capacity after 15 times that circulates is approximately 1650mAh/g, and capability retention is only about 52%.Can find out thus, battery in embodiment 1 obviously has more excellent charging and discharging capacity and cycle performance relative to the battery in comparative example 2, this result shows that PANi and RGO effectively can suppress the change in volume of silicon materials and improve its conductivity, thus the specific capacity of battery is increased, cycle performance improves.Simultaneously compared with comparative example 1, also demonstrate that PANi can improve the cycle performance of elemental silicon greatly.
The TGA figure of the negative material that Figure 14 is embodiment 1, comparative example 1 and comparative example 2 provide, and the contrast TGA listing RGO, PANi material schemes, from wherein finding out that PANi loses its most of quality at 400-600 DEG C, RGO loses its most of quality at 450-600 DEG C.On the contrary, n-Si particle is gained in weight and is formed SiO after 600 DEG C
x, when 800 DEG C, retain 113.3% of proper mass.N-Si/PANi and n-Si/PANi/RGO material all loses quality gradually after thermogravimetric analysis, retains 90.3% and 73.9% of proper mass when 800 DEG C respectively.Thermogravimetric analysis shows, n-Si/PANi/RGO material has special thermal gravimetric analysis results, can differentiate the composition of synthesis accordingly.The mass ratio of Si, PANi, RGO three in n-Si/PANi/RGO material can also be calculated by analysis meter according to the thermogravimetric result of PANi, RGO, n-Si particle, n-Si/PANi and n-Si/PANi/RGO material.In the present embodiment, the mass ratio of Si, PANi, RGO three in active component is 68:23:9.
The high rate performance of the battery that Figure 15 is embodiment 1, comparative example 1 and comparative example 2 provide is to the relation comparison diagram of cycle-index.When current density is increased to 500mA/g the specific capacity of n-Si/PANi/RGO material to reduce and be stabilized in ~ specific capacity of 2200mAh/g, n-Si/PANi material reduces and is stabilized in 1500mAh/g, the specific capacity of n-Si material reduces and is stabilized in 1000mAh/g.Continue to increase current density, the specific capacity of n-Si material drops to ~ 500mAh/g, but n-Si/PANi/RGO material and n-Si/PANi material maintain the reversible capacity of 1300mAh/g and 800mAh/g respectively, illustrate that the interpolation compound of PANi and RGO has facilitation to the high rate performance promoting silicon materials.When current density is down to 200mA/g, the specific capacity of n-Si/PANi/RGO material returns to 70.4% of raw capacity, n-Si material and n-Si/PANi material return to 35.6% and 50.1% respectively, illustrate that n-Si/PANi/RGO material has better high rate performance compared to other bi-materials.
The above embodiments are only used to allow those skilled in the art understand the present invention and to provide preferred embodiment.The present invention is not limited in above-mentioned specific embodiment.Any those skilled in the art easily full of beard and improvement all within inventive concept of the present invention.
Claims (14)
1. a cell negative electrode material, is characterized in that: the component of described negative material comprises active material elemental silicon, redox graphene and polyaniline.
2. negative material according to claim 1, is characterized in that: the mass ratio of described active material elemental silicon, polyaniline and redox graphene is K1:K2:K3, and wherein K1 is 55 ~ 81, K2 be 18 ~ 28, K3 is 7 ~ 11.
3. negative material according to claim 1, is characterized in that: described active material elemental silicon comprises nano level spheric granules.
4. negative material according to claim 1, is characterized in that: the active material elemental silicon in described negative material has two-layer coating layer, and ground floor is polyaniline, and the second layer is redox graphene.
5. a battery cathode, is characterized in that: described battery cathode comprises as the negative material in claim 1-4 as described in any one.
6. a battery, comprises positive pole, negative pole, electrolyte and barrier film, it is characterized in that: described negative pole comprises as the negative material in claim 1-4 as described in any one.
7. a preparation method for cell negative electrode material, is characterized in that: described preparation method comprises the steps:
Add elemental silicon particle and surfactant in deionized water, carry out ultrasonic disperse;
In-situ polymerization prepares the mixture of polyaniline-coated silicon grain;
Prepare redox graphene solution;
Redox graphene solution is added in the mixture of polyaniline-coated silicon grain;
Filter, wash and the dry mixture processing silicon, polyaniline and redox graphene.
8. preparation method according to claim 7, is characterized in that: described elemental silicon comprises nano level spheric granules.
9. preparation method according to claim 7, is characterized in that: described surfactant comprises DTAB and n-butanol.
10. preparation method according to claim 7, is characterized in that: the mixture preparing described polyaniline-coated silicon grain comprises the steps:
Aniline monomer and Bronsted acid is added in elemental silicon dispersion liquid;
Ice bath adds the aqueous solution of oxidant ammonium persulfate under stirring, in-situ polymerization generates the mixture of polyaniline-coated silicon grain.
11. preparation methods according to claim 10, is characterized in that: described Bronsted acid comprises one or more in hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, oxalic acid, citric acid, tartaric acid, p-methyl benzenesulfonic acid, camphorsulfonic acid, sulfosalicylic acid, dodecyl sodium sulfonate, DBSA, naphthalene sulfonic acids, dinonylnaphthalene sulfonic acid, polystyrolsulfon acid, polyvinyl sulfonic acid, sulfamic acid and aminobenzenesulfonic acid.
12. preparation methods according to claim 7, is characterized in that: the mode of described filtration comprises vacuum filtration or centrifugal filtration.
13. preparation methods according to claim 7, is characterized in that: described washing carries out successively with ethanol, water and hydrochloric acid.
14. preparation methods according to claim 7, is characterized in that: described drying process carries out under vacuum, and the temperature range of described drying process is 65-75 DEG C, and the time range of dry process is 10-14 hour.
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| CN104835963A (en) * | 2015-04-24 | 2015-08-12 | 中南大学 | Lithium ion battery composite anode material and preparation method thereof |
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| CN110707288B (en) * | 2018-07-10 | 2021-07-02 | 北京理工大学 | Silicon-based negative electrode active material and preparation method and application thereof |
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