CN101210118A - Method for preparing carbon coating graphite/silicon oxide composite material - Google Patents
Method for preparing carbon coating graphite/silicon oxide composite material Download PDFInfo
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Abstract
A preparation method for a carbon encapsulated graphite/silicon oxide composite material comprises the following steps that: a uniform mixture of the graphite and silicate and/or silicon ester solution is contacted with acidoid so as to ensure that the uniform mixture forms sizing agent which is dried, products obtained by the sizing agent being dried are mixed with carbon matrix precursor solution, the mixture of products and carbon matrix precursor is dried and the dried solid is baked under the protect of inert gases. The carbon enclosed graphite/silicon oxide composite material made by the preparation method provided by the invention has excellent synthetical electrochemical properties. Compared with the composite material prepared by the prior art, the carbon enclosed graphite/silicon oxide composite material made by the preparation method obviously improves the specific capacity, the first efficiency for charge-discharge and the capacity conservation rate after the 20 times of circulation.
Description
Technical field
The invention relates to a kind of preparation method of graphite/silicon oxide composite material of carbon parcel.
Background technology
Present commercial lithium ion battery adopts lithium transition-metal oxide/graphite system as negative active core-shell material mostly, though the chemical property excellence of this class system, but it is lower itself to store up the lithium ability, particularly the theoretical capacity of carbon class negative active core-shell material only is 372 MAH/grams, and so low capacity has been difficult to adapt to the miniaturization development of various portable electric appts and the electromobile demand to large vol, superpower chemical power source at present.Therefore, studying at present a kind of new performance that the negative active core-shell material of height ratio capacity more improves lithium ion battery that has, meeting the need of market.
To studies show that of non-carbon negative active core-shell material, have the metal or alloy class material of many high storage lithium performances to use as negative active core-shell material, wherein silicon becomes the most attractive a kind of because of having embedding lithium specific storage big (theoretical specific capacity can reach 4200 MAH/grams) and the low characteristics such as (less than 0.5 volts) of embedding lithium current potential.Yet, there is serious volume effect in silicon in the process of removal lithium embedded, owing to volumetric expansion produces bigger mechanical stress, the cyclical stability of the battery that causes using silicon to do negative active core-shell material is poor in the charge and discharge process of battery, thereby has hindered the industrial applications of silicon.
The volume effect problem that solves silicon materials has two kinds of methods usually: the one, and depositing silicon film on the collector of battery cathode, the advantage of this method is not need to add other component in the electrode, shortcoming is to be not suitable for scale operation, and when the thickness of silicon film surpasses 1 micron, the diffusion length of lithium ion increases, and resistance increases.The 2nd, prepare siliceous matrix material, modal is silicon/carbon composite.Though the affiliation that adds of carbon causes the specific storage of matrix material to descend to some extent, the specific storage after reducing still is much higher than the specific storage of carbon itself, therefore still can be used as the desirable surrogate of carbon class negative active core-shell material.Silicon/carbon composite has two kinds of structures, and a kind of is " cake type " structure, is about to silicon grain and at first is dispersed in (mainly being pitch, resin etc.) in the organic precursor, organism is carried out high temperature carbonization again and handles, and obtains silicon/carbon composite.
CN03116070 discloses a kind of silumin/carbon composite, this material is dispersible carrier with carbon, silicon/al proportion is 1 in silicon, the aluminium alloy: 1-5: between 1, the content of sial active material in matrix material is 10-50 weight %, described dispersible carrier and carbon and graphite powder are scattered in the carbon base body that cracking carbon forms, and the mass ratio of powdered graphite and aluminium alloy powder is 2: 3.This preparation methods is; silica flour and aluminium powder are mixed at the ball milling method under the protective atmosphere; the powder of mixing was handled 30-120 minute in 600-1000 ℃ under protection of inert gas; form the active body precursor; organic polymer as one of dispersible carrier precursor; be dissolved in and be cracked into carbon in the organic solvent; Graphite Powder 99 joins in the cracked carbon; mix; then the active body precursor of making is joined in the cracked carbon; the formation slurry is uniformly dispersed; with slurry after room temperature vapors away organic solvent, in the sealed reaction system, temperature reaction under rare gas element or protection of inert gas; temperature of reaction is at 600-1000 ℃, reaction times 60-300 minute.The mechanical stability of this matrix material has improved, and has improved the electron conduction of material, but because the alloy material particle of high temperature solid-state method preparation is bigger, the cyclical stability of material is relatively poor.
CN1667855A discloses a kind of battery cathode active substance, and this negative electrode active material comprises silica-based mixture and carbonaceous material, and this silica-based mixture comprises Si oxide (SiO
x, wherein, x≤1.5) and at least a element, described element is selected from one or more among B, P, Li, Ge, Al, the V, and described carbonaceous material is selected from crystalline carbon and/or decolorizing carbon, and the weight ratio of silica-based mixture and carbonaceous material is 30: 70-70: 30.This preparation methods is, with silicon-dioxide, Si and contain at least a compound in B compound, P-compound, Li compound, Ge compound, Al compound, the V compound, by mixture being heat-treated and quenching, prepare silica-based mixture, then with silica-based mixture, adopt chemical vapor deposition, with the indefinite-form carbon material coating thereon, prepare this negative electrode active material.But, since in this material the preparation of Si oxide by SiO
2With the preparation of Si simple substance, agglomeration appears in the dispersion process easily, and the Si oxide particle diameter that makes simultaneously is bigger, has influenced the stable circulation performance of this negative electrode active material.
Negative material particle according to the preparation of the way of prior art is bigger, and the stress that has produced because of the Si oxide volume change when therefore having reduced the height doff lithium makes that the cycle performance of negative active core-shell material of preparation is relatively poor.
Summary of the invention
The negative material particle that the objective of the invention is in order to overcome the prior preparation method preparation is bigger, the shortcoming of the negative active core-shell material cycle performance difference of feasible preparation, a kind of preparation method that can make silicon-dioxide be distributed to the graphite/silicon oxide composite material of the carbon parcel in the middle of the graphite with Nano grade is provided, graphite/the silicon oxide composite material of the carbon parcel of the feasible preparation of feasible preparation has the cyclical stability excellent characteristics, also has higher specific storage simultaneously.
The invention provides a kind of preparation method of graphite/silicon oxide composite material of carbon parcel; this method comprises graphite is contacted with acidic substance with the uniform mixture of the solution of silicate and/or silicon ester; make described uniform mixture form slurry; the slurry that drying obtains; the product that drying is obtained mixes with carbon matrix precursor solution; drying, and under protection of inert gas the dried solid of roasting.
Method provided by the invention is by adding graphite in the preparation process of silicon-dioxide, because the bigger and stronger adsorptive power of particle diameter of graphite, thereby hindered the silicic acid sol generation agglomeration that makes by after alkalimetal silicate and/or soluble silicon compound and the acidic substance reaction, thereby silicon-dioxide is distributed in the middle of the graphite, the stress that has produced because of the Si oxide volume change when therefore having reduced the height doff lithium with Nano grade.In addition, nanometer grade silica is compared the particle dia that also reduces mixture greatly with existing micron silica, make with the graphite/silicon oxide composite material of the carbon parcel prepared battery as negative electrode active material, not only have higher specific storage, also have excellent cyclical stability simultaneously.
Embodiment
Graphite/silicon oxide composite material preparation method according to carbon parcel provided by the invention, by alkalimetal silicate and/or soluble silicon compound are dissolved in the solvent, add the graphite mixing then, add acidic substance again, form slurry, it is 2-5 that the add-on of acidic substance makes the pH value of slurry of formation.
Among the present invention, described acidic substance can be various acidic substance, for example, be selected from the solution, organic acid, organic acid solution, sour gas of the solution of mineral acid, mineral acid, acid inorganic salt, acid inorganic salt one or more, described sour gas can be carbonic acid gas and/or sulfurous gas.Under the preferable case, described acidic substance are selected from one or more in hydrochloric acid, acetate, the ammonia chloride.
According to method provided by the invention, although a spot of alkalimetal silicate and/or soluble silicon compound and carbonaceous material can be realized purpose of the present invention, but preferable case, in the uniform mixture of the solution of graphite and silicate and/or silicon ester, with respect to 100 weight part graphite, in silicon-dioxide, the content of described silicate and/or silicon ester is the 5-70 weight part, is preferably the 15-45 weight part.
Among the present invention, in described silicate and/or the silicon ester solution, be benchmark with the weight of solution, in silicon-dioxide, silicate/or the content of silicon ester be 1-30 weight %, under the preferable case, in silicon-dioxide, silicate/or the content of silicon ester be 5-20 weight %.Described solvent can be water and/or various conventional organic solvent, for example can be selected from water, ethanol, acetone, tetrahydrofuran (THF), the propylene oxide one or more, as solvent, make solvent for mensuration dissolubility silicic salt preferably water for silicic acid lipid preferred alcohol and/or acetone.
Among the present invention, described alkalimetal silicate is selected from one or more in water glass, potassium silicate, the lithium silicate, if select for use alkalimetal silicate as raw material, in the preparation process, need the product that obtains with the deionized water wash drying 3-6 time, to remove alkalimetal ion, make to detect in the finally prepd composite materials to be as the criterion less than alkalimetal ion.Described silicon ester is selected from one or more in tetraethoxysilance, tetramethoxysilance, positive silicic acid third fat, if selecting silicon ester for use is raw material, does not then need to use deionized water wash.
Among the present invention, described graphite can be the graphite of lithium ion battery field routine, and under the preferable case, described graphite is average particle diameter D
50Be the graphite of 10-30 micron, further preferred graphite is average particle diameter D
50Graphite for the 18-22 micron.
Among the present invention, in the uniform mixture of the solution of graphite and silicate and/or silicon ester and the acidic substance contact process, temperature is 5-80 ℃, and the reaction times is 5-60 minute, and under the preferable case, temperature is 20-60 ℃, and the reaction times is 5-30 minute.
Among the present invention, graphite contacts with acidic substance with the uniform mixture of the solution of silicate and/or silicon ester, make described uniform mixture form slurry, the slurry that drying obtains, in the product and carbon matrix precursor solution mixing process that drying is obtained, with respect to 100 weight part graphite, in carbon simple substance, the content of carbon matrix precursor is 1-15 weight %, and the content of preferred carbon matrix precursor is 2-8 weight %.Described carbon matrix precursor is selected from carbohydrate and/or high molecular polymer, for example one or more in glucose, polyoxyethylene glycol, resol, Resins, epoxy, the pitch etc.
Among the present invention, described roast can carry out according to the method for well known to a person skilled in the art.For example, can heat 3-12 hour down at 900-1400 ℃ earlier under rare gas element and/or reducing gas, quench treatment obtains graphite/silicon oxide composite material that carbon coats then.
Among the present invention, described rare gas element can be the gas of neutral element in nitrogen, hydrogen and the periodic table of elements, as in helium, neon, argon gas and the xenon one or more.Described heating is preferably with the heating of 0.5-10 ℃/minute speed.Described quenching feeds the purpose that the current that are equal to or less than room temperature reach quenching with water cooling apace by the furnace wall skin.
The following examples will the present invention is described further.
Embodiment 1
This embodiment is used to illustrate the preparation method of the graphite/silicon oxide composite material of carbon parcel provided by the invention.
4.12 grams are contained Na
2O, (8.2 weight %), SiO
2The water glass solution of (20 weight %) is prepared 400 milliliters the aqueous solution, adds 4.5 gram median size D in solution
50Be 18 microns Graphite Powder 99, stir, be warming up to 70 ℃, handled 6 minutes, the dilute hydrochloric acid that slowly drips concentration when stirring fast and be 0.2 mol is to pH value 3.0, stirs also that heated and stirred becomes pasty state, dry black powder.Soak powder with 500 ml deionized water, but mild heat is treated to pour out the top layer settled solution after the solution clarification, clean so repeatedly 6 times, to wherein adding 1 gram glucose (carbon content is 40 weight %), add 200 ml waters and stir and heat evaporate to dryness, oven dry then to pasty state.The material of gained is warming up to 1200 ℃ with 5 ℃/minute under argon shield, is incubated 5 hours,, promptly obtain graphite/silicon composite A1 that carbon coats with 500K/ quench treatment second.
Comparative Examples 1
With 4.5 gram median size D
50Be 18 microns graphite, 0.824 gram SiO 2 powder and 2 gram glucose join in 200 ml waters, and stirring and heating evaporation are dried to pasty state.The material of gained is warming up to 1200 ℃ with 5 ℃/minute under argon shield, is incubated 5 hours,, obtain reference matrix material CA1 with 500K/ quench treatment second.
Embodiment 2
This embodiment is used to illustrate the preparation method of the graphite/silicon oxide composite material of carbon parcel provided by the invention.
2.06 grams are contained Na
2O, (8.2 weight %), SiO
2The water glass solution of (20 weight %) is prepared 400 milliliters the aqueous solution, adds 4.75 gram median size D in solution
50Be 22 microns Graphite Powder 99, stir, be warming up to 70 ℃, handled 6 minutes, the ammonium chloride solution that slowly drips concentration when stirring fast and be 0.5 mol is to pH value 4.0, stirs also that heated and stirred becomes pasty state, dry black powder.Soak powder with 500 ml deionized water, but mild heat, treat to pour out the top layer settled solution after the solution clarification, clean so repeatedly 3 times, be 2500 polyoxyethylene glycol (carbon content is 54.5 weight %) (fluffy chemical industry is moistened in Shanghai) to wherein adding 1 gram mean polymerisation degree then, add 200 ml waters and stir and heat evaporate to dryness, oven dry to pasty state.The material of gained is warming up to 1180 ℃ with 5 ℃/minute under argon shield, is incubated 6 hours,, promptly obtain graphite/silicon composite A2 that carbon coats with 500K/ quench treatment second.
Embodiment 3
This embodiment is used to illustrate the preparation method of the graphite/silicon oxide composite material of carbon parcel provided by the invention.
3 gram tetraethoxysilances are dissolved in 100 ml ethanols, add 4.5 gram stone median size D
50Be 20 microns Graphite Powder 99 and 0.5 gram resol (carbon content is 70.5 weight %), stir, be warming up to 60 ℃, handled 7 minutes, the ammonium chloride solution that slow dropping concentration is 0.5 mol when stirring fast is to pH value 3.5, stir and heated and stirred become pasty state, dry black powder.The material of gained is warming up to 1250 ℃ with 5 ℃/minute under argon shield, is incubated 4 hours,, promptly obtain graphite/silicon composite A3 that carbon coats with 500K/ quench treatment second.
Embodiment 4-6
With thickness is that 0.06 millimeter, diameter are that 16 millimeters, weight are that the metal lithium sheet of 0.0064 gram is a negative electrode active material, with the modified polypropene barrier film, with the LiPF of 1 mol
6Solution is electrolytic solution, and graphite/silicon composite A1-A3, conductive carbon black and polyvinylidene difluoride (PVDF) that the carbon that is made by the foregoing description 1-3 with 0.125 gram coats are positive electrode material with 70: 10: 20 mixture of weight ratio, make button cell S1-S3.
According to following step measurements electrochemical specific capacity: battery S1-S3 shelved change into to 0.2 volt of voltage with 0.2 milliampere of electric current after 60 minutes, then respectively with 1 milliampere, 0.8 milliampere, 0.7 milliampere, 0.6 milliampere constant current discharge to 0.005 volt, after shelving 30 minutes, again with 0.5 milliampere, 0.3 milliampere, 0.1 milliampere, 0.06 milliampere, 0.03 milliampere constant current discharge to 0.005 volt, shelve after 30 minutes with 0.3 milliampere of electric current constant current charge, record charges to cell voltage and reaches 2.5 volts time, according to standard capacity (MAH)=charging current (milliampere) * duration of charging of button cell (hour) calculate the standard capacity of button cell, standard capacity promptly gets the electrochemical specific capacity of button cell negative electrode active material (graphite/silicon composite A1-A3 that carbon containing coats) divided by the weight of the negative electrode active material (graphite/silicon composite A1-A3 that carbon containing coats) of button cell, the ratio of electrochemical specific storage and initial charge electrochemistry capacitance is the first charge-discharge efficiency of material first, and the result is as shown in table 1.
The cycle performance of the graphite/silicon composite A1-A3 that coats according to following step measurements carbon containing: with 6.39 gram LiCoO
2Being positive active material, is barrier film with the modified polypropene barrier film, with the LiPF of 1 mol
6Solution is electrolytic solution, be negative electrode active material with 1.50 the gram siliceous composite sample A1-A3, conductive carbon black and the polyvinylidene difluoride (PVDF) that make by the foregoing description 1-3 with 70: 10: 20 mixture of weight ratio respectively, make 043450A type (the design cell container is 800 MAHs) secondary lithium battery S4-S6.
With 80 milliamperes (0.1C) to 043450A type secondary lithium battery S4-S6, carried out constant current charge 960 minutes, deboost is 4.2 volts, shelved after the charging 15 minutes, and, repeated the above-mentioned step 20 time of discharging and recharging with 160 milliamperes of (0.2C) constant current discharges to 3.0 volt, loading capacity after the record circulation 20 times, calculate this capacity and the ratio of loading capacity first, be the capability retention after the circulation 20 times, the result is as shown in table 1.
Comparative Examples 2
Method according to embodiment 4-6, the reference matrix material CA1 of Comparative Examples 1 preparation is prepared into reference button cell CS1 and reference 043450A type battery CS2 respectively, the specific storage and the first charge-discharge efficiency that reference button cell CS1 are carried out battery detect, reference 043450A type battery CS2 is carried out 20 capability retentions after the circulation to be detected, as a result, as shown in table 1.
Table 1
| The embodiment numbering | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative Examples 2 |
| The matrix material numbering | ?A1 | ?A2 | ?A3 | ?CA1 |
| Specific storage (MAH/gram) | ?483 | ?465 | ?472 | ?389 |
| First charge-discharge efficiency (%) | ?84 | ?85 | ?84 | ?60 |
| 20 circulation back capability retentions (%) | ?89 | ?90 | ?89 | ?48 |
As can be seen from Table 1, graphite/the silicon composite that the invention provides the carbon containing coating of method preparation has superior comprehensive electrochemical, and the capability retention after specific storage, first charge-discharge efficiency and 20 circulations all is significantly improved than the matrix material of prior art for preparing.
Claims (13)
1. the preparation method of the graphite/silicon oxide composite material of carbon parcel; it is characterized in that; this method comprises graphite is contacted with acidic substance with the uniform mixture of the solution of silicate and/or silicon ester; make described uniform mixture form slurry; the slurry that drying obtains; the product that drying is obtained mixes with carbon matrix precursor solution, drying, and under protection of inert gas the dried solid of roasting.
2. method according to claim 1, wherein, the add-on of described acidic substance makes and forms pH value of slurry is 2-5.
3. method according to claim 1 and 2, wherein, described acidic substance are selected from one or more in the solution, organic acid, organic acid solution, sour gas of the solution of mineral acid, mineral acid, acid inorganic salt, acid inorganic salt.
4. method according to claim 3, wherein, described acidic substance are selected from one or more in hydrochloric acid, ammonia chloride, the acetate.
5. method according to claim 1, wherein, graphite and silicate/or the uniform mixture of the solution of silicon ester in, with respect to 100 weight part graphite, in silicon-dioxide, the content of described silicate and/or silicon ester is the 5-70 weight part.
6. method according to claim 5, wherein, in silicon-dioxide, described silicate/or silicon ester solution in, be benchmark with the solution weight, the content of silicate and/or silicic acid fat is 1-30 weight %.
7. method according to claim 6, wherein, described solvent is water and/or organic solvent.
8. method according to claim 1, wherein, described silicate is selected from one or more in water glass, potassium silicate, the lithium silicate, and this method also is included in after the slurry that drying obtains, the product that obtains with the deionized water wash drying.
9. method according to claim 1, wherein, described silicon ester is selected from one or more in tetraethoxysilance, tetramethoxysilance, positive silicic acid third fat.
10. method according to claim 1, wherein, described graphite is average particle diameter D
50Graphite for the 10-30 micron.
11. method according to claim 1, wherein, the condition that described uniform mixture contacts with acidic substance comprises that temperature is 5-80 ℃, and the reaction times is 5-60 minute.
12. method according to claim 1, wherein, when the product that drying is obtained mixed with carbon matrix precursor solution, with respect to 100 weight part graphite, in carbon simple substance, the content of carbon matrix precursor was 1-15 weight %.
13. method according to claim 1, wherein, described carbon matrix precursor is selected from carbohydrate and/or high molecular polymer.
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| CN109054447A (en) * | 2018-08-24 | 2018-12-21 | 河南理工大学 | A kind of preparation method of humic acid charcoal-silica two-phase compounded mix |
| CN110876959A (en) * | 2019-12-09 | 2020-03-13 | 怀化学院 | Solid carbon sulfonic acid catalyst and preparation method thereof, and tributyl citrate and preparation method thereof |
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