CN103165862A - High-performance negative material of lithium ion cell and preparation method of material - Google Patents
High-performance negative material of lithium ion cell and preparation method of material Download PDFInfo
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Abstract
The invention discloses a high-performance negative material of a lithium ion cell. The negative material comprises a Si-SiOx/C/DC composite system which comprises a C base, porous Si-SiOx adhered to the base, carbon nano tubes distributed in the base and the Si-SiOx, and an outermost pyrolytic carbon coating layer. The invention also discloses a preparation method of the negative material. The negative material is high in specific capacity and good in cycling stability, thus being suitable for a high-energy-density cell of a portable mobile terminal or a digital product.
Description
Technical field
The invention belongs to the materialogy field, be specifically related to a kind of lithium ion battery high-specific-capacity silicon carbon composite negative pole material.
Background of invention
Lithium ion battery from the nineties in last century begin practical since, the outstanding advantages such as voltage is high owing to having, energy density is large, good cycle, self discharge amount are little, memory-less effect have been widely used in the fields such as mobile terminal, digital product and portable mobile apparatus, electric automobile and energy-accumulating power station.But along with the birth of intelligent mobile terminal electronic equipment, at present lithium ion battery is difficult to satisfy its long-time instructions for use, and due to the finite volume of mobile terminal, so the exploitation of high-specific energy battery product is extremely urgent.
Commercial lithium battery used adopts cobalt acid lithium/graphite, nickel-cobalt-manganese ternary/graphite system mostly at present, but the theoretical lithium storage content of graphite itself is lower, has been difficult to the breakthrough of the capacity of obtaining by the improvement of battery process.Elemental silicon has ten theoretical specific capacity that are multiple times than native graphite as negative material
(4200mAh/g), be subject to the general concern of material circle and research.Yet there is following problem in elemental silicon as battery cathode active substance: (1) forms Li under full power state in embedding lithium process
22Si
5Alloy phase, the change in volume of material reaches more than 300%.The mechanical internal stress that so huge bulk effect produces can make electrode active material and collector peel off gradually, and the silicon activity mutually itself also can efflorescence in addition, thereby has lost and the electrically contacting of collector, and causes cycle performance of battery to descend rapidly; (2) conductivity is low.Silicon itself is semi-conducting material, and conductivity is low only 6.7 * 10
-4Scm-1 need add conductive agent to improve the electronic conductivity of silicon active matter; (3) be difficult to form stable SEI film.In charge and discharge process, huge bulk effect can cause constantly having silicon exposed in electrolyte, is difficult to form stable SEI film, causes electroactive material cycle performance fast-descending.
In the patent application of many Si-C composite negative pole materials, mostly to improve the lithium storage content of negative material by methods such as the mixing of silicon and graphite, coating, doping, but the scattering problem of nanoscale silica flour thoroughly is not resolved always, causes electrode part subregion inactivation.The present invention adopts high-energy ball milling method to prepare the Si-SiOx presoma, introduce submicron metal reduction SILICA FUME in mechanical milling process, obtain having with Si the SiOx of certain compatibility, when having realized good dispersion, the porousness feature of presoma has reduced the internal stress that silicon produces to a certain extent when bulk effect occurs.The present invention adopts organic RESEARCH OF PYROCARBON to coat, and not only makes the Si-SiOx of porous and carbon matrix material that better bonding is arranged, and has also eliminated the dangling bonds on the carbon base body, has also avoided activated silica to contact with the direct of electrolyte, has improved the cyclical stability of battery.
Summary of the invention
In order to solve the above-mentioned technical problem of silicium cathode material, the invention provides a kind of high performance lithium ion battery silicon-carbon cathode material and preparation technology thereof.Negative material of the present invention is the Si-SiOx/C/DC compound system, and it is that Si-SiOx with submicron order is scattered in constitutionally stable material with carbon element uniformly, utilizes carbon base body the cushioning effect of volumetric expansion to be improved the cycle life of silicium cathode.
A kind of high performance lithium ionic cell cathode material comprises carbon base body, is dispersed in Si-SiOx in matrix, is distributed in carbon nano-tube and outermost RESEARCH OF PYROCARBON coating layer in matrix and Si-SiOx:
Wherein, above-mentioned carbon base body is one or more in native graphite, Delanium, carbonaceous mesophase spherules (MCMB), hard carbon;
Described Si-SiOx removes metal by silica flour, SILICA FUME, super-fine metal powder and a kind of porous compound of forming after the high energy mechanical chemical reaction;
The average diameter of described carbon nano-tube is that 10～100nm, draw ratio are (8～24): 1 nanofiber;
The organic RESEARCH OF PYROCARBON coating layer of described outermost layer is the organic carbon coating layer that organic substance forms after polycondensation, carbonization.
Second purpose of the present invention is to provide a kind of preparation method of this high-performance negative material, and it comprises the following steps:
(1) high-purity silicon powder, SILICA FUME, submicron metal, dispersant are mixed by a certain percentage, carry out ball milling in ball grinder;
(2) with step (1) product with 50～150 ℃ of vacuumize 1～24h; Product is sintering in nitrogen and/or argon gas;
(3) step (2) product is carried out pickling, filtration, vacuum drying;
(4) the C matrix is carried out high temperature oxidation process in air atmosphere;
(5) step (3) product and step (4) product are mixed by proper proportion, join be added with carbon nano-tube RESEARCH OF PYROCARBON solution in, the low speed secondary ball milling disperses;
(6) with the heating of step (5) product, stir the evaporation desolventizing;
(7) with sintering in step (6) non-oxidizing atmosphere, organic RESEARCH OF PYROCARBON carbonization treatment, and naturally cool to room temperature, realize that organic RESEARCH OF PYROCARBON coats;
(8) step (7) product is sieved with 200～500 eye mesh screens, obtain the Si-O-C composite negative pole material.
Negative material of the present invention can satisfy the requirement to cell high-capacity and high circulation.Preparation method of the present invention is simple, goes for technical scale production.
Description of drawings
Fig. 1 is the crystallogram (adopting Cuk α target emanation) of the prepared high power capacity silico-carbo composite material of embodiment 1;
Fig. 2 is the SEM figure of the prepared Si-C composite material of embodiment 1.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with drawings and Examples, the present invention is described in more detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
A kind of high performance carbon carbon negative electrode material of lithium ion cell comprises the C matrix, is bonded in Si-SiOx-C in matrix, is distributed in carbon nano-tube and outermost organic RESEARCH OF PYROCARBON coating layer in matrix and Si-SiOx-C.
The present embodiment is matrix used is native graphite, and the average grain diameter of described native graphite is 6～30 μ m;
Described Si-SiOx-C is a kind of compound that is formed with the oxide of rare HCl removal aluminium or aluminium after the high energy mechanical chemical reaction by silica flour, SILICA FUME, ultra-fine aluminium, carbon nano-tube;
Described carbon nano-tube is that average diameter is that 10～100nm, draw ratio are (8～24): 1 finely disseminated nanofiber;
Described RESEARCH OF PYROCARBON coating layer is the RESEARCH OF PYROCARBON coating layer that organic substance forms after high temperature pyrolysis, carbonization, and the coating thickness of described organic RESEARCH OF PYROCARBON coating layer is 50～300nm;
In the present invention, submicron order cavernous Si-SiOx composite particles Uniform Dispersion also is bonded in the surface of native graphite matrix, and utilize organic RESEARCH OF PYROCARBON that it is coated, and forms the RESEARCH OF PYROCARBON coating layer of complete densification.Be dispersed with the carbon nanotube conducting network between composite particles and coating layer and between composite particles, forming height ratio capacity silico-carbo composite material of the present invention.
The specific area of the preferred nucleocapsid structure composite particles of the present invention is 0.8～30m
2/ g, more preferably 0.9～10m
2/ g.
The coating thickness of preferred substrate coating layer of the present invention is 50～300nm, more preferably 80～200nm;
In the present invention, the specific capacity size of composite material is determined by the ratio of Si-SiOx compound and native graphite, preferred 1: 100～50: 100 of the present invention, more preferably 10: 100～30: 100; The ratio of the preferred SILICA FUME of the present invention and silica flour is 1: 100～100: 100, more preferably 10: 100～50: 100; The ratio of the preferred aluminium powder of the present invention and SILICA FUME is 10: 100～100: 100, more preferably 30: 100～60: 100; The mass ratio of the preferred carbon nano-tube of the present invention and Si-SiOx-C is 0.1: 100～20: 100, more preferably 0.5: 100～5: 100; The mass ratio that the present invention coats preferred organic RESEARCH OF PYROCARBON and Si-SiOx-C is 1: 100～50: 100, more preferably 5: 100～30: 100.
The preparation method of negative material of the present invention, it comprises the steps:
(1) will there be high-purity silicon powder, SILICA FUME, superfine aluminium power, dispersant to mix by a certain percentage;
(2) step (1) material is positioned in ball grinder, adds a certain proportion of zirconia ball, high-energy ball milling;
(3) step (2) product is carried out vacuumize;
(4) with step (3) product sintering in non-oxide atmosphere;
(5) step (4) product is carried out pickling, filtration, vacuum drying;
(6) with commercialization C raw material high-temperature oxydation certain hour in air atmosphere;
(7) step (5) product and step (6) product are mixed by proper proportion, join in the certain density RESEARCH OF PYROCARBON solution that is added with carbon nano-tube, the low speed secondary ball milling disperses;
(8) with the heating of step (7) product, stir and desolventizing;
(9) with sintering in step (8) non-oxidizing atmosphere, the RESEARCH OF PYROCARBON carbonization treatment, and naturally cool to room temperature, realize that RESEARCH OF PYROCARBON coats;
(10) with the screening of step (9) product, obtain the Si-C composite negative pole material.
Organic RESEARCH OF PYROCARBON coating layer raw material is known in those skilled in the art.Organic RESEARCH OF PYROCARBON commonly used has glucose, sucrose, polyvinyl chloride, phenolic resins, furfural resin, poly furfuryl alcohol, polyacrylonitrile, coal tar pitch, petroleum asphalt etc.Preferably sucrose of the present invention.
The solvent that the present invention adopts is selected from one or more of deionized water, ethanol, hexane, octane, cyclohexane, benzene, toluene, biphenyl, naphthalene, anthracene, pyridine, oxolane.The preferred deionized water of the present invention.
The average diameter of the carbon nano-tube that the present invention adopts is that 20nm, average length are draw ratio 8: 1～12: 1.
The preferred non-oxidizing atmosphere of the present invention is one or both of nitrogen and argon gas.
The preferred operations of step (1) is: high-purity silicon powder, SILICA FUME, aluminium powder are mixed by a certain percentage, and add alcohol as dispersant.Ultrasonic dispersion 30-120 minute;
The preferred operations of step (2) is: will change in stainless steel jar mill in step (1) product, and add the zirconia ball of 0.2～20mm, ratio of grinding media to material example 10: 1～20: 1, after deaeration at 150～450r/min ball milling, 4～48h, more preferably 350～450r/min ball milling, 12～24h;
The preferred operations of step (3) is: with the product elimination zirconia ball of step (2), 60～100 ℃ of vacuum dryings, mechanical crushing;
The preferred operations of step (4) is: with step (3) product under the protection of industrial nitrogen, 400～900 ℃ of sintering 1～10 hour;
The preferred operations of step (5) is: step (4) product is added in rare HCl, and stirring at normal temperature 10min～6h filters and washs to neutral;
The preferred operations of step (6) is: with 200～600 ℃ of oxidations 2～4 hours in air atmosphere of native graphite raw material;
The preferred operations of step (7) is: step (5) and step (6) product are added in the organic RESEARCH OF PYROCARBON dispersion liquid that is dispersed with carbon nano-tube after proportioning by a certain percentage, in stainless steel jar mill, 150～200r/min ball milling is 1～8 hour, more preferably 2～4 hours; Ratio of grinding media to material example 5: 1～20: 1, more preferably 10: 1～15: 1; Zirconia sphere diameter 5～20mm, more preferably 10～20mm;
The preferred operations of step (8) is: after step (7) product is considered deoxidation zirconium ball, and dry out solvent under dynamic condition, preferred 60～150 ℃ of temperature, more preferably 80～120 ℃;
The preferred operations of step (9) is: with step (8) product 400～1000 ℃ of lower sintering 2～10h under the industrial nitrogen atmosphere protection, more preferably 600～900 ℃ of sintering 4～8h, then naturally cool to room temperature;
The preferred operations of step (10) is: step (9) product is crossed 150～500 mesh sieves, more preferably 250～350 mesh sieves..
Below in conjunction with specific embodiment, the present invention is further elaborated.
Embodiment 1
Each component is as follows:
High pure metal silica flour: 11.0g (99.9%), average grain diameter is 1.0～2.5 μ m;
SILICA FUME: 4.8g (99%), average grain diameter 3～10 μ m;
Superfine metal aluminium powder: 2.2g (99%), average grain diameter 5～10 μ m;
Rare HCl:120g (10% mass concentration);
Carbon nano tube paste: 40g (LITHIUM BATTERY, water system 5% concentration), average diameter is 20～30nm, average aspect ratio 8～12;
Native graphite: 89g (spherical graphite, LITHIUM BATTERY) average grain diameter is 6～12 μ m, interlamellar spacing d
002Be 0.3353～0.3354nm;
Sucrose: 25g (food grade).
The preparation method is as follows:
(1) get high pure metal silica flour, SILICA FUME, superfine aluminium power, and with 100ml alcohol as the ultrasonic dispersion of dispersant 1h;
(2) above-mentioned dispersion is changed in stainless steel jar mill, and to add the 300g diameter be 0.2～10mm zirconia ball, use the argon gas deaeration, 400r/min batch (-type) ball milling 16h on planetary ball mill after the preservative film sealing;
(3) with step (2) product elimination zirconia ball, vacuum drying, pulverizing, the lower 670 ℃ of sintering 4h of industrial nitrogen protective condition, and naturally cool to room temperature;
(4) step (3) product is added in rare HCl, stir 2h, filter and wash to neutral;
(5) with native graphite 400 ℃ of sintering 2h in air atmosphere, naturally cool to room temperature;
(6) with sucrose dissolved in 200ml distilled water, add carbon nano tube paste and step (4), (5) product, add ball grinder after ultrasonic dispersion 30min, and to add the 400g diameter be the zirconia ball of 5～20mm, 200r/min ball milling 2h on planetary ball mill;
(7) with after step (6) product filtering zirconia ball, solvent evaporated under stirring;
(8) step (7) product is warming up to 750 and constant temperature 6h with the programming rate of 3～5 ℃ under industrial nitrogen protection, 900 ℃ of constant temperature 2h naturally cool to room temperature, cross 300 mesh sieves.
Make at last the composite silica carbon negative pole material, be denoted as A.
Comparative Examples 1
With embodiment 1 difference be: without " the rare HCl washing of step (4) ";
Other steps are as embodiment 1.The silicon-carbon cathode material that makes at last is denoted as B1.
Comparative Examples 2
With embodiment 1 difference be: (1) step did not have " adding superfine aluminium power ", without " the rare HCl washing of step (4) ";
Other steps are with embodiment 1.The silicon-carbon cathode material that makes at last is denoted as B2.
Comparative Examples 3:
With embodiment 1 difference be: (1) step did not have " adding SILICA FUME ";
Other steps are with embodiment 1.The silicon-carbon cathode material that makes at last is denoted as B3.
Comparative Examples 4
With embodiment 1 difference be: " step (1) does not add aluminium powder and SILICA FUME ", without " the rare HCl washing of (3) 670 ℃ of sintering of step and step (4) " process;
Other steps are with embodiment 1.The silicon-carbon cathode material that makes at last is denoted as B4.
Electrochemical property test
the preparation of simulated battery: water is as dispersion, 1.5 part sodium carboxymethylcellulose (CMC) and 2.5 parts of butadiene-styrene rubber (SBR) are as binding agent, the super-P of 2 parts is as conductive agent, the active material A1 of 94 parts, A2, A3 and B, stirring is polished into uniform sizing material and is coated on Copper Foil after drying moisture, 80 ℃ of vacuum baking 12h and compressing tablet are as electrode to be measured, metal lithium sheet is to electrode, electrolyte is the LiPF6 (EC+DMC mixes with the volume ratio of 1: 1) of 1mol/L, barrier film adopts the cellgard2400 film, be assembled into the button cell of CR2025 in the argon shield glove box.
Reversible specific capacity test: at LAND CT2001A battery testing cashier's office in a shop with the electric current of 0.1C with above-mentioned button cell from the 0.02V initial charge to 1.2V, calculate specific capacity by the charging capacity that records, computing formula is: specific capacity=take off first lithium capacity/active material quality.The results are shown in Table 1.
First charge-discharge efficiency test: with the constant current of 0.1C～0.002C, above-mentioned button cell is discharged to 0.02V cashier's office in a shop at LAND CT2001A battery testing, then the constant current with 0.1C charges to 1.2V with battery, record discharge capacity and initial charge capacity first, thereby the calculating first charge-discharge efficiency, computing formula is: discharge capacity * 100% of first charge-discharge efficiency=initial charge capacity/first.The results are shown in Table 1.
Loop test:, under 25 ℃ of constant temperatures, button cell is carried out charge-discharge test with the 0.1C electric current between 0.02-1.2V at LAND CT2001A battery testing cashier's office in a shop.Circulate 50 weeks or volume lowering to initial capacity below 70%, stop test.The results are shown in Table 1.
Table 1: physical and chemical performance and button cell performance test
As can be seen from Table 1, in Comparative Examples, B3 compares with embodiment A with B4, and reversible specific capacity, first charge-discharge efficiency all present B4＞B3＞A first, illustrates that the introducing of SiOx has increased its irreversible specific capacity first; In Comparative Examples, B1, B2 compare with embodiment A with B3, and pilot process is introduced the raising that reactive metal is conducive to cyclical stability, and reactive metal or its compound cause capacity that very fast decay is arranged without removal.The comprehensive above data of analyzing illustrate that the cycle performance of high-specific-capacity silicon carbon negative pole of the present invention is greatly improved.
Be only below that feature of the present invention is implemented example, protection range of the present invention is not constituted any limitation.The equal exchange of all employings or equivalence are replaced and the technical scheme of formation, within all dropping on rights protection scope of the present invention.
Claims (10)
1. high performance lithium ionic cell cathode material, described negative material comprises that specific area is 1～30m
2The Si-SiOx/C/DC compound system of/g, described compound system comprise the C matrix, be bonded in Si-SiOx in matrix, be distributed in carbon nano-tube and outermost organic RESEARCH OF PYROCARBON coating layer in matrix and Si-SiOx-C, it is characterized in that:
(1) described C matrix is one or more in native graphite, Delanium, carbonaceous mesophase spherules MCMB, hard carbon through oxidation processes;
(2) described Si-SiOx is to be that 0.01～10 μ silica flour, particle diameter are that 0.1～10 μ SILICA FUME and super-fine metal powder are removed a kind of porous compound that metal forms after the high energy mechanical chemical reaction by particle diameter;
(3) average diameter of described carbon nano-tube is that 5～100nm, draw ratio are 2～25: 1 nanofiber;
(4) the organic RESEARCH OF PYROCARBON coating layer of described outermost layer is the carbon coating layer that organic substance forms after polycondensation, carbonization.
2. negative material according to claim 1, it is characterized in that: described super-fine metal powder is one or more in aluminium powder, glass putty, zinc powder, magnesium powder, calcium powder and titanium valve, described super-fine metal powder particle diameter is for being 0.1～10 μ m.
3. negative material according to claim 1, it is characterized in that: described organic RESEARCH OF PYROCARBON raw material is selected from one or more in glucose, sucrose, polyvinyl chloride, phenolic resins, furfural resin, poly furfuryl alcohol, polyacrylonitrile, coal tar pitch and petroleum asphalt.
4. the preparation method of the described negative material of claims 1 to 3 any one, is characterized in that comprising the steps:
(1) high-purity silicon powder, SILICA FUME, submicron metal, dispersant are mixed by a certain percentage, carry out ball milling in ball grinder;
(2) with step (1) product with 50～150 ℃ of vacuumize 1～24h; Product is sintering in nitrogen and/or argon gas;
(3) step (2) product is carried out pickling, filtration, vacuum drying;
(4) the C matrix is carried out high temperature oxidation process in air atmosphere;
(5) step (3) product and step (4) product are mixed by proper proportion, join be added with carbon nano-tube RESEARCH OF PYROCARBON solution in, the low speed secondary ball milling disperses;
(6) with the heating of step (5) product, stir the evaporation desolventizing;
(7) with sintering in step (6) non-oxidizing atmosphere, organic RESEARCH OF PYROCARBON carbonization treatment, and naturally cool to room temperature, realize that organic RESEARCH OF PYROCARBON coats;
(8) step (7) product is sieved with 200～500 eye mesh screens, obtain the Si-O-C composite negative pole material.
5. the preparation method of negative material according to claim 4, it is characterized in that: the ratio of described Si-SiOx compound and native graphite is 1: 100～100: 10, the ratio of described SILICA FUME and silica flour is 1: 100～100: 100, the ratio of described aluminium powder and SILICA FUME is 1: 100～100: 100, and the mass ratio of described carbon nano-tube and Si-SiOx-C is 0.1: 100～20: 100; The mass ratio of described organic RESEARCH OF PYROCARBON and Si-SiOx-C is 1: 100～50: 100.
6. the preparation method of negative material according to claim 4, it is characterized in that: the ball milling of described step (1) is planetary milling, described zirconia ball diameter is 0.1～50mm, and described Ball-milling Time is 1～30 hour, described drum's speed of rotation 150～500r/min.
7. the preparation method of negative material according to claim 4, it is characterized in that: in described step (3) acid cleaning process, acid used is one or more that are selected from hydrochloric acid, sulfuric acid and the nitric acid that mass fraction is 3%-15%, and pickling time is 30～300 minutes.
8. the preparation method of negative material according to claim 4, it is characterized in that: the high-temperature oxydation temperature of described step (4) C matrix is 200～500 ℃, and oxidization time is 0.5～10h.
9. the preparation method of negative material according to claim 4 is characterized in that: the solvent of the organic RESEARCH OF PYROCARBON of described step (5) dissolving select water, ethanol, benzene, toluene, how, one or more in anthracene, cyclohexane, trichloroethylene, acetone, ethyl acetate, pyridine and oxolane.
10. the preparation method of negative material according to claim 4, it is characterized in that: the temperature that described step (6) stirs desolventizing is 80～250 ℃, and mixing time is 1～10 hour.
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