CN103137951A - Lithium ion battery stannum-based composite anode material and preparation method thereof - Google Patents
Lithium ion battery stannum-based composite anode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a lithium ion battery stannum-based composite anode material, which comprises the following steps: (1) mixing metal stannum powder, graphite, a dispersant and water to obtain slurry, wherein the average particle size D50 of the stannum powder and graphite is 460-612 nm; (2) performing spray granulation to obtain particles; (3) mixing a conductive polymer solution with a mass volume concentration of 8-18 g/L with the particles, wherein the using amount of the conductive polymer is 5-10 wt% of the total amount of the metal stannum powder and the graphite, stirring, performing centrifugation separation, drying, sieving by using a sieve of more than 300 meshes to obtain the undersize. The invention also discloses a lithium ion battery stannum-based composite anode material prepared by the method, which has a high specific capacity, and good cycle performance.
Description
Technical field
The present invention relates to the battery electrode material field, relate in particular to a kind of tin-based composite anode materials for lithium-ion batteries and preparation method thereof.
Background technology
The commercial Li-ion battery negative pole is generally graphite type material or with the material of carbon as matrix, material with carbon element has cycle performance preferably as lithium ion secondary battery negative pole, substantially, reach the level of its theoretical limit capacity 372mAh/g, but it obviously can't satisfy people to the demand of high-capacity electrode.The characteristics such as tin-based material has high-quality specific energy and volumetric specific energy, and low price has no side effect, and processing is synthetic relatively easy have caused people's extensive concern.But simple tin-based material produces larger volume contraction when removal lithium embedded reacts, electrode material efflorescence easy to crack, and inner forfeiture of active material electrically contacts, and causes material electrochemical performance to worsen, and cycle performance is poor, and irreversible capacity is high first.Also there is same problem in its oxide.
For improving the chemical property of tin base cathode material, the thinking of research concentrates on mainly that material nano, alloying, coating are processed, mesoporous or micropore is inlayed the aspects such as tin or ashbury metal.The researcher has done a lot of related works, Ning Linjian (" being used for the tin of lithium ion battery negative material/carbon composite research ", journal, 2008,9,915-919) adopt diffuse-aggregate method to coat poly-contraposition divinylbenzene on the surface of tin oxide, then pyrolysis has prepared tin particles homodisperse tin-carbon composite in carbon base body.He Xiangming (" synthesis of spherical nano tin encapsulated pyrolytic polyacrylonitrile composite anode material for Li-ion batteries ", Solid State ionics, 2007,178,833-836) with liquid phase reduction, tin is coated in polyacrylonitrile, after 300 ℃ of low temperature pyrogenations, polyacrylonitrile dehydrogenation denitrogenation forms the conjugated chain structure, tin particles is evenly distributed on after pyrolysis in collective, has improved the cyclical stability of metallic tin.But the tin base cathode material of these improvement still has a segment distance from business-like requirement.
Summary of the invention
Technical problem to be solved by this invention is in order to overcome the poor defective of existing Tin Composite Material cycle performance, provides that a kind of specific capacity is high, the tin-based composite anode materials for lithium-ion batteries of good cycle and preparation method thereof.
The present invention solves the problems of the technologies described above by the following technical programs.
The invention provides a kind of preparation method of tin-based composite anode materials for lithium-ion batteries, it comprises the following steps:
(1) with metallic tin powder, graphite, dispersant and water mixed-shaped form slurry, the average grain diameter D of wherein said glass putty or described graphite
50Be 460-612nm;
(2) mist projection granulating gets particle;
(3) be that the conductive polymer solution of 8-18g/L mixes with described particle with the mass body volume concentrations, stir centrifugation; dry; cross the above sieve of 300 orders, extracting screen underflow gets final product, and the quality of wherein said conducting polymer accounts for the 5-10wt% of metallic tin powder and graphite powder total weight.
In a better embodiment of the present invention, described preparation method's concrete operation step is:
1. glass putty raw material, graphite raw material and described dispersant are mixed with water, Ultrafine Grinding gets described slurry, the average grain diameter D of particle in described slurry
50Be 460-612nm;
2. mist projection granulating gets described particle;
3. described conductive polymer solution is mixed with described particle, stir, centrifugation, drying is crossed the above sieve of 300 orders, and extracting screen underflow gets final product.
Described Ultrafine Grinding is the conventional lapping mode of this area, generally adopts ultra-fine ball milling.
In the present invention, described graphite is the conventional graphite that uses in this area, is generally Delanium and/or native graphite.
The consumption of described glass putty and described graphite is this area conventional amount used, and preferably the weight ratio of described glass putty and described graphite is 0.2-0.4: 1.
Described dispersant is the conventional dispersant that uses in this area, is preferably one or more in PVP (english abbreviation PVP), sodium carboxymethylcellulose (english abbreviation CMC), polyvinyl alcohol (english abbreviation PVA) and polyethylene glycol (english abbreviation PEG); Be more preferably that the PVP of 5200-7200, sodium carboxymethylcellulose, the weight average molecular weight that weight average molecular weight is 5300-7400 are 5.8 * 10 for weight average molecular weight
4-8.5 * 10
4Polyvinyl alcohol and one or more of the weight average molecular weight polyethylene glycol that is 4700-6800.
Described dispersant dosage is the conventional amount used of this area, and preferably, described dispersant accounts for the 1-3wt% of described glass putty and described graphite gross mass.
Preferably, the quality of described water is 7-9 with the ratio of the gross mass of described glass putty, described graphite and described dispersant: 1.
Described mist projection granulating is this area routine techniques, its charging rate and be the conventional parameter of this area into and out of the air port temperature; Preferably, the charging rate 3.2-4.8kg/h of described mist projection granulating, the intake air temperature of described mist projection granulating are 180-220 ℃, and the air outlet temperature of described mist projection granulating is 100-130 ℃.
Preferably, the average grain diameter D of described particle
50Be 7.5-11.6 μ m.
Described conducting polymer is the conventional conducting polymer that uses in this area, is preferably any in polyaniline (english abbreviation Pan), polypyrrole (english abbreviation PPy) or polythiophene (english abbreviation PTh).The molecular weight of described polyaniline, described polypyrrole and described polythiophene is the conventional molecular weight that uses in this area.
The solvent of described conductive polymer solution is the conventional use in this area, can make the homodisperse solvent of conducting polymer, is preferably 1-METHYLPYRROLIDONE.
Described stirring is this area routine techniques, and preferably, the time of described stirring is 2-3 hour, and the speed of described stirring is 80-100rpm.
Described centrifugal condition is the centrifugal condition of this area routine, and preferably, described centrifugal speed is 4000-5000rpm.
Described drying is this area conventional drying mode, and preferably, the temperature of described drying is 80-120 ℃.
In the present invention, the average grain diameter D of prepared tin-based composite anode materials for lithium-ion batteries
50Be 11-14.5 μ m.
The present invention also provides a kind of tin-based composite anode materials for lithium-ion batteries that is made by above-mentioned preparation method.
Preferably, the average grain diameter D of described tin-based composite anode materials for lithium-ion batteries
50Be 11-14.5 μ m.
On the basis that meets this area general knowledge, above-mentioned each optimum condition, but combination in any namely get the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available getting all.
Positive progressive effect of the present invention is:
The tinbase composite negative pole material that preparation method of the present invention obtains has the above specific discharge capacity of 400mAh/g, and enclosed pasture efficient is more than 85% first, and after charge and discharge cycles 100 times, capability retention surpasses 90%.
Description of drawings
Fig. 1 is that embodiment 1 obtains the SEM figure that negative material amplifies 3000 times.
Fig. 2 is the cyclic curve figure that embodiment 5 obtains negative material.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example according to conventional method and condition, or is selected according to catalogue.
Ball mill in the present invention is available from the Wuxi prosperous powder equipment of celebrating Co., Ltd, and model is CXM-230 type nano level superfine ball mill;
Spray drying device is available from the super spray drying machinery of Wuxi City richness factory, and model is DIS-5 type Highspeedcentrifugingandsprayingdrier.
In following embodiment, sodium carboxymethylcellulose reaches chemical industry Co., Ltd available from Jiangyin City's perseverance, sticking sodium carboxymethylcellulose during commodity are by name; Polyvinyl alcohol is available from Guangzhou river in Henan Province Sheng chemical industry Co., Ltd, and commodity are called polyvinyl alcohol 1788; Polyethylene glycol is available from Nanjing WeiEr chemical engineering Co., Ltd, and commodity are called Macrogol 6000; PVP is available from upper nautical mile specialization industry science skill Co., Ltd, and commodity are called PVPK30; Electrically conductive polyaniline, polypyrrole, polythiophene are self-control, wherein:
Preparation method's reference " electric conductivity of polythiophene/multi-wall carbon nano-tube composite material " of polythiophene (chemical journal, 2007,65,2923-2928);
The preparation method of polyaniline is with reference to " polyaniline/Fe
3O
4Preparation and the sign of nano composite material in initial neutral solution " (functional material, 2008,39,68-72);
The preparation method of polypyrrole is with reference to " the lithium iron phosphate positive material preparation and property research that polypyrrole coats " (Shanghai Communications University's Engineering Master paper, Yang Yang, in December, 2009);
All the other are common commercial goods.
Embodiment 1
With metallic tin powder (D
50=48 μ m) (available from Shanghai Shanshan Science and Technology Co., Ltd, commodity are called YT7-38, D for 80g, Delanium 400g
50=26 μ m), the 4.8g sodium carboxymethylcellulose mixes with 4L water, the average grain diameter D of Ultrafine Grinding 4 hours particle to the slurry
50Be 512nm, the charging rate that spray drying device is set is 3.2kg/h, is respectively 180 ℃, 100 ℃ into and out of the air port temperature, and ball milling disposed slurry mist projection granulating is obtained average grain diameter D
50It is the spheric granules of 8.2 μ m, under room temperature, it is mixed with 1-METHYLPYRROLIDONE that 3L is dissolved with electrically conductive polyaniline, wherein electrically conductive polyaniline accounts for the 5wt% of glass putty and graphite total weight, 80rpm stirred 2 hours, the particle that the 4500rpm centrifugation obtains obtains average grain diameter D through 90 ℃ of vacuumizes, mistake 300 mesh sieves
50Be 12.2 μ m tinbase composite negative pole materials (seeing Fig. 1).
The electrochemical property test method:
Utilize the performance of the tin-based composite anode materials for lithium-ion batteries of the present embodiment preparation for check, prepare lithium ion battery with this cell negative electrode material.
Negative material wherein: Super-P conductive agent: SBR binding agent: the weight ratio of CMC thickener is 93: 2: 2.5: 2.5, and add appropriate 1-METHYLPYRROLIDONE to mix, be coated on copper foil of affluxion body after stirring and oven dry 12 hours under vacuum.Be assembled into button cell with the lithium sheet after taking out in vacuum glove box, electrolyte is for containing 1MLiPF
6EC-DEC (volume ratio is 1: 1) solution.Carry out under electro-chemical test constant temperature, voltage 0.005-2.0V, current density is 15mA/g.Test result shows that the first discharge specific capacity of the tinbase composite negative pole material of preparation is 448mAh/g, and the initial charge specific capacity is 390mAh/g, and enclosed pasture efficient is that 87%, 100 capability retention after circulation is 90%.
Embodiment 2
With metallic tin powder (D
50=48 μ m) (available from Shanghai Shanshan Science and Technology Co., Ltd, commodity are called MGS-2, D for 120g, native graphite 400g
50=18 μ m), the 10.4g polyvinyl alcohol mixes with 4L water, the average grain diameter D of Ultrafine Grinding 4 hours particle to the slurry
50Be 563nm, the charging rate that spray drying device is set is 3.8kg/h, is respectively 200 ℃, 100 ℃ into and out of the air port temperature, and the slurry mist projection granulating after ball milling obtains average grain diameter D
50Be 8.7 μ m spheric granules, again it is joined under room temperature in the 1-METHYLPYRROLIDONE that 2.9L is dissolved with the 52g electrically conductive polyaniline, wherein electrically conductive polyaniline accounts for the 10wt% of glass putty and graphite total weight, 100rpm stirred 2 hours, and the particle that the 4000rpm centrifugation obtains obtains average grain diameter D through 80 ℃ of vacuumizes, mistake 300 mesh sieves
50It is the tinbase composite negative pole material of 13.5 μ m.Electrochemical property test result with embodiment 1 shows, the first discharge specific capacity of the tinbase composite negative pole material of preparation is 485mAh/g, and the initial charge specific capacity is 417mAh/g, and enclosed pasture efficient is that 86%, 100 capability retention after circulation is 91%.
Embodiment 3
With metallic tin powder (D
50=48 μ m) (available from Shanghai Shanshan Science and Technology Co., Ltd, commodity are called YT7-38, D for 160g, Delanium 400g
50=26 μ m), 16.8g PVP and 5L water mixes, the average grain diameter D of Ultrafine Grinding 5 hours particle to the slurry
50Be 460nm, the charging rate that spray drying device is set is 4.8kg/h, is respectively 220 ℃, 120 ℃ into and out of the air port temperature, and the slurry mist projection granulating after ball milling obtains average grain diameter D
50It is the spheric granules of 7.6 μ m, again it is joined under room temperature in the 1-METHYLPYRROLIDONE that 4L is dissolved with electrically conductive polyaniline, wherein electrically conductive polyaniline accounts for the 8wt% of glass putty box graphite total weight, 80rpm stirred 2 hours, the particle that the 5000rpm centrifugation obtains obtains average grain diameter D through 100 ℃ of vacuumizes, mistake 300 mesh sieves
50It is the tinbase composite negative pole material of 11 μ m.Electrochemical property test result with embodiment 1 shows, the first discharge specific capacity of the tinbase composite negative pole material of preparation is 527mAh/g, and the initial charge specific capacity is 453mAh/g, and enclosed pasture efficient is that 86%, 100 capability retention after circulation is 91%.
Embodiment 4
With metallic tin powder (D
50=48 μ m) (available from Shanghai Shanshan Science and Technology Co., Ltd, commodity are called MGS-1, D for 80g, native graphite 400g
50=16 μ m), 4.8g polyethylene glycol and 4L water mixes, the average grain diameter D of Ultrafine Grinding 5 hours particle to the slurry
50Be 523nm, the charging rate that spray drying device is set is 4kg/h, is respectively 210 ℃, 130 ℃ into and out of the air port temperature, and after ball milling, the material mist projection granulating obtains average grain diameter D
50It is the spheric granules of 9.7 μ m, again it is joined under room temperature in the 1-METHYLPYRROLIDONE that 3L is dissolved with polypyrrole PPy, wherein polypyrrole PPy accounts for the 5wt% of glass putty and graphite total weight, 100rpm stirred 3 hours, the particle that the 4500rpm centrifugation obtains obtains average grain diameter D through 100 ℃ of vacuumizes, mistake 300 mesh sieves
50It is the tinbase composite negative pole material of 14.2 μ m.Electrochemical property test result with embodiment 1 shows, the first discharge specific capacity of the tinbase composite negative pole material of preparation is 436mAh/g, and the initial charge specific capacity is 375mAh/g, and enclosed pasture efficient is that 85%, 100 capability retention after circulation is 92%.
Embodiment 5
With metallic tin powder (D
50=45 μ m) (available from Shanghai Shanshan Science and Technology Co., Ltd, commodity are called F tin-1, D for 160g, Delanium 400g
50=25 μ m), 5.6g sodium carboxymethylcellulose, 5.6g polyvinyl alcohol and 4L water mixes, the average grain diameter D of Ultrafine Grinding 5 hours particle to the slurry
50Be 612nm, the charging rate that spray drying device is set is 3.8kg/h, is respectively 220 ℃, 130 ℃ into and out of the air port temperature, and ball milling disposed slurry mist projection granulating is obtained average grain diameter D
50It is the spheric granules of 11.6 μ m, again it is joined under room temperature in the 1-METHYLPYRROLIDONE that 3L is dissolved with polypyrrole, wherein polypyrrole accounts for the 8wt% of glass putty and graphite total weight, 100rpm stirred 2 hours, the particle that the 4500rpm centrifugation obtains obtains average grain diameter D through 90 ℃ of vacuumizes, mistake 300 mesh sieves
50It is the tinbase composite negative pole material of 14.5 μ m.With the electrochemical property test result of embodiment 1 as shown in Figure 2, the first discharge specific capacity of the tinbase composite negative pole material of preparation is 520mAh/g, and the initial charge specific capacity is 458mAh/g, and enclosed pasture efficient is that 88%, 100 capability retention after circulation is 91%.
Embodiment 6
With metallic tin powder (D
50=45 μ m) (available from Shanghai Shanshan Science and Technology Co., Ltd, commodity are called MGS-1, D for 120g, native graphite 400g
50=16 μ m), 7.8g sodium carboxymethylcellulose, 7.8g polyethylene glycol and 4L water mixes, the average grain diameter D of Ultrafine Grinding 5 hours particle to the slurry
50Be 536nm, the charging rate that spray drying device is set is 4.5kg/h, is respectively 190 ℃, 110 ℃ into and out of the air port temperature, the ball milling disposed slurry is carried out mist projection granulating obtain average grain diameter D
50It is the spheric granules of 7.8 μ m, under room temperature, it is joined in the 1-METHYLPYRROLIDONE that 2.9L is dissolved with the 52g polypyrrole, wherein polypyrrole accounts for the 10wt% of glass putty and graphite total weight, 90rpm stirred 2 hours, the particle that the 5000rpm centrifugation obtains divides through 90 ℃ of vacuumizes, 300 mesh sieves, obtains average grain diameter D
50It is the tinbase composite negative pole material of 11.9 μ m.Electrochemical results with embodiment 1 shows, crossing the first discharge specific capacity that 300 mesh sieves obtain the tinbase composite negative pole material is 472mAh/g, and the initial charge specific capacity is 406mAh/g, and enclosed pasture efficient is that 86%, 100 capability retention after circulation is 90%.
Embodiment 7
With metallic tin powder (D
50=45 μ m) (available from Shanghai Shanshan Science and Technology Co., Ltd, commodity are called YT7-38, D for 160g, Delanium 400g
50=26 μ m), 5.6g sodium carboxymethylcellulose and 4L water mixes, the average grain diameter D of Ultrafine Grinding 6 hours particle to the slurry
50Be 490nm, the charging rate that spray drying device is set is 4.1kg/h, is respectively 200 ℃, 110 ℃ into and out of the air port temperature, and ball milling disposed slurry mist projection granulating is obtained average grain diameter D
50Be the spheric granules of 8.3 μ m, it joined under room temperature in the 1-METHYLPYRROLIDONE that 3.2L is dissolved with the 56g polythiophene again, 80rpm stirred 2.5 hours, the particle that the 4800rpm centrifugation obtains through 100 ℃ of vacuumizes, cross 300 mesh sieves, obtain average grain diameter D
50It is the tinbase composite negative pole material of 13.6 μ m.Electrochemical property test result with embodiment 1 shows, the first discharge specific capacity of the tinbase composite negative pole material of preparation is 532mAh/g, and the initial charge specific capacity is 458mAh/g, and enclosed pasture efficient is that 86%, 100 capability retention after circulation is 92%.
Embodiment 8
With metallic tin powder (D
50=48 μ m) (available from Shanghai Shanshan Science and Technology Co., Ltd, commodity are called F tin-4, D for 120g, Delanium 400g
50=22 μ m), 10.4g polypyrrole alkane ketone and 4L water mixes, the average grain diameter D of Ultrafine Grinding 5 hours particle to the slurry
50Be 563nm, the charging rate that spray drying device is set is 3.9kg/h, is respectively 180 ℃, 100 ℃ into and out of the air port temperature, with ball milling disposed slurry mist projection granulating, obtains average grain diameter D
50Be the spheric granules of 9.2 μ m, then under room temperature, it joined in the 1-METHYLPYRROLIDONE that 3L is dissolved with the 41.6g polythiophene, 80rpm stirred 2 hours, the particle that the 4200rpm centrifugation obtains through 80 ℃ of vacuumizes, cross 300 mesh sieves, obtain average grain diameter D
50It is the tinbase composite negative pole material of 13.5 μ m.Electrochemical property test result with embodiment 1 shows, the first discharge specific capacity of the tinbase composite negative pole material of preparation is 476mAh/g, and the initial charge specific capacity is 424mAh/g, and enclosed pasture efficient is that 89%, 100 capability retention after circulation is 90%.
Embodiment 9
With metallic tin powder (D
50=45 μ m) (available from Shanghai Shanshan Science and Technology Co., Ltd, commodity are called MGS-1, D for 80g, native graphite 400g
50=16 μ m), 14.4g polyethylene glycol and 4L water mixes, the average grain diameter D of Ultrafine Grinding 6 hours particle to the slurry
50Be 582nm, the charging rate that spray drying device is set is 4.6kg/h, is respectively 200 ℃, 120 ℃ into and out of the air port temperature, with ball milling disposed slurry mist projection granulating, obtains average grain diameter D
50Be 8.6 μ m spheric granules, then under room temperature, it joined in the 1-METHYLPYRROLIDONE NMP that 3L is dissolved with the 24g polythiophene, 90rpm stirred 2 hours, the particle that the 5000rpm centrifugation obtains through 100 ℃ of vacuumizes, cross 300 mesh sieves, obtain average grain diameter D
50It is the tinbase composite negative pole material of 12.3 μ m.Electrochemical results with embodiment 1 shows, the first discharge specific capacity of the tinbase composite negative pole material of preparation is 431mAh/g, and the initial charge specific capacity is 379mAh/g, and enclosed pasture efficient is that 88%, 100 capability retention after circulation is 91%.
The comparative example 1
With metallic tin powder (D
50=48 μ m) (available from Shanghai Shanshan Science and Technology Co., Ltd, commodity are called YT7-38, D for 80g, Delanium 400g
50=26 μ m), 4.8g sodium carboxymethylcellulose and 4L water mixes, the average grain diameter D of Ultrafine Grinding 4 hours particle to the slurry
50Be 512nm, the charging rate that spray drying device is set is 3.2kg/h, is respectively 180 ℃, 100 ℃ into and out of the air port temperature, and ball milling disposed slurry mist projection granulating is obtained spheric granules, then 90 ℃ of vacuum drying chambers, and 300 mesh sieves divide and obtain average grain diameter D
50It is the tinbase composite negative pole material of 8.5 μ m.
Electrochemical results with embodiment 1 shows, the first discharge specific capacity of the tinbase composite negative pole material of preparation is 492mAh/g, and the initial charge specific capacity is 359mAh/g, and enclosed pasture efficient is that 73%, 100 capability retention after circulation is 71%.
The comparative example 2
With metallic tin powder (D
50=45 μ m) (available from Shanghai Shanshan Science and Technology Co., Ltd, commodity are called MGS-1, D for 120g, native graphite 400g
50=16 μ m), 7.8g sodium carboxymethylcellulose, 7.8g polyethylene glycol and 4L water mixes, the average grain diameter D of Ultrafine Grinding 5 hours particle to the slurry
50Be 526nm, the charging rate that spray drying device is set is 4.5kg/h, is respectively 190 ℃, 110 ℃ into and out of the air port temperature, the ball milling disposed slurry is carried out mist projection granulating obtain spheric granules, then 90 ℃ of vacuum drying chambers, and 300 mesh sieves divide and obtain average grain diameter D
50It is the tinbase composite negative pole material of 8.1 μ m.
Electrochemical results with embodiment 1 shows, crossing the first discharge specific capacity that 300 mesh sieves obtain the tinbase composite negative pole material is 517mAh/g, and the initial charge specific capacity is 366mAh/g, and enclosed pasture efficient is that 71%, 100 capability retention after circulation is 66%.
Claims (10)
1. the preparation method of a tin-based composite anode materials for lithium-ion batteries, it comprises the following steps:
(1) with metallic tin powder, graphite, dispersant and water mixed-shaped form slurry, the average grain diameter D of wherein said glass putty or described graphite
50Be respectively 460-612nm;
(2) mist projection granulating gets particle;
(3) be that the conductive polymer solution of 8-18g/L mixes with described particle with the mass body volume concentrations, the quality of wherein said conducting polymer accounts for the 5-10wt% of metallic tin powder and graphite powder total weight, stirs; centrifugation; drying is crossed the above sieve of 300 orders, and extracting screen underflow gets final product.
2. preparation method as claimed in claim 1, is characterized in that, described preparation method carries out in the steps below: glass putty raw material, graphite raw material and described dispersant are mixed with water, and Ultrafine Grinding gets described slurry, the average grain diameter D of particle in described slurry
50Be 460-612nm; Step described in carry out claim 1 successively (2) and step (3).
3. preparation method as claimed in claim 1, is characterized in that, the weight ratio of described glass putty and described graphite is 0.2-0.4: 1; Described dispersant accounts for the 1-3wt% of described glass putty and described graphite gross mass; The quality of described water is 7-9 with the ratio of the gross mass of described glass putty, described graphite and described dispersant: 1.
4. preparation method as claimed in claim 1 or 2, is characterized in that, described dispersant is one or more in PVP, sodium carboxymethylcellulose, polyvinyl alcohol and polyethylene glycol; Be preferably that the PVP of 5200-7200, sodium carboxymethylcellulose, the weight average molecular weight that weight average molecular weight is 5300-7400 are 5.8 * 10 for weight average molecular weight
4-8.5 * 10
4Polyvinyl alcohol and one or more of the weight average molecular weight polyethylene glycol that is 4700-6800.
5. preparation method as claimed in claim 1 or 2, is characterized in that, the charging rate 3.2-4.8kg/h of described mist projection granulating, the intake air temperature of described mist projection granulating are 180-220 ℃, and the air outlet temperature of described mist projection granulating is 100-130 ℃.
6. preparation method as claimed in claim 1 or 2, is characterized in that, the average grain diameter D of described particle
50Be 7.5-11.6 μ m.
7. preparation method as claimed in claim 1 or 2, is characterized in that, described conducting polymer is polyaniline, polypyrrole or polythiophene; The solvent of described solution is 1-METHYLPYRROLIDONE.
8. preparation method as claimed in claim 1 or 2, is characterized in that, the time of described stirring is 2-3 hour, and the speed of described stirring is 80-100rpm; Described centrifugal speed is 4000-5000rpm; The temperature of described drying is 80-120 ℃.
9. preparation method as described in any one in claim 1-8, is characterized in that the average grain diameter D of prepared tin-based composite anode materials for lithium-ion batteries
50Be 11-14.5 μ m.
10. tin-based composite anode materials for lithium-ion batteries that is made by any preparation method in claim 1-9, preferably, its average grain diameter D
50Be 11-14.5 μ m.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103825011A (en) * | 2014-02-28 | 2014-05-28 | 苏州路特新能源科技有限公司 | Preparation method of tin of lithium ion battery and conductive polymer composite cathode material membrane |
| CN105186003A (en) * | 2015-09-24 | 2015-12-23 | 上海大学 | Preparation method of high-capacity lithium-ion battery anode material |
| WO2017032166A1 (en) * | 2015-08-25 | 2017-03-02 | 田东 | Preparation method for lithium battery negative-electrode slurry doped with tin powder |
| CN108878797A (en) * | 2017-09-22 | 2018-11-23 | 久兆新能源科技股份有限公司 | A kind of high compacted density lithium iron phosphate positive material and anode pole piece |
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| CN101017893A (en) * | 2006-02-08 | 2007-08-15 | 深圳市比克电池有限公司 | A tin carbon compound electrode material for lithium ion battery cathode and preparing method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103825011A (en) * | 2014-02-28 | 2014-05-28 | 苏州路特新能源科技有限公司 | Preparation method of tin of lithium ion battery and conductive polymer composite cathode material membrane |
| CN103825011B (en) * | 2014-02-28 | 2016-04-06 | 苏州路特新能源科技有限公司 | The tin of lithium ion battery and the preparation method of conducting polymer composite negative pole material film |
| WO2017032166A1 (en) * | 2015-08-25 | 2017-03-02 | 田东 | Preparation method for lithium battery negative-electrode slurry doped with tin powder |
| CN105186003A (en) * | 2015-09-24 | 2015-12-23 | 上海大学 | Preparation method of high-capacity lithium-ion battery anode material |
| CN108878797A (en) * | 2017-09-22 | 2018-11-23 | 久兆新能源科技股份有限公司 | A kind of high compacted density lithium iron phosphate positive material and anode pole piece |
| CN108878797B (en) * | 2017-09-22 | 2021-09-07 | 久兆新能源科技股份有限公司 | High-compaction-density lithium iron phosphate positive electrode material and positive electrode plate |
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| Publication number | Publication date |
|---|---|
| CN103137951B (en) | 2016-08-31 |
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