CN101777651B - Silicon anode material and preparation method thereof and lithium battery using silicon anode material - Google Patents
Silicon anode material and preparation method thereof and lithium battery using silicon anode material Download PDFInfo
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- CN101777651B CN101777651B CN200910104890XA CN200910104890A CN101777651B CN 101777651 B CN101777651 B CN 101777651B CN 200910104890X A CN200910104890X A CN 200910104890XA CN 200910104890 A CN200910104890 A CN 200910104890A CN 101777651 B CN101777651 B CN 101777651B
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Abstract
The invention provides an anode material of a lithium battery, which comprises an active substance and a volume buffering agent. The active substance is coated or partly coated on the surfaces of the particles of the volume buffering agent. The active substance is silicon. The volume buffering agent is silicon dioxide. The invention also provides a preparation method for the anode material, wherein silicon dioxide of powder and powder of a carbon reducing agent which are subjected to pretreatment are subjected to vacuum high temperature sintering; and based on the total weight of the silicon dioxide and the carbon reducing agent, the weight of the carbon reducing agent occupies 16.67 to 35.8 percent of the total weight. The anode material provided by the invention has good cycle performance and high capacity.
Description
Technical field
The invention belongs to the lithium ion battery field.The lithium battery that the present invention is specifically related to a kind of silicon-based anode material and preparation method thereof and uses this material.
Background technology
But lithium ion battery receives widely with a series of significant advantages such as its operating voltage is high, specific energy is big, in light weight, volume is little, have extended cycle life, memory-less effect fast charging and discharging and non-environmental-pollution and paying close attention to.Along with the continuous development of lithium ion battery, people also have higher requirement to the performance of lithium ion battery.In this case, research and development have more that the lithium ion battery material of height ratio capacity better cycle ability has very important strategic importance.
Silica-base material is the most promising negative material that can satisfy lithium ion battery requirement of new generation at present.Silicon materials are compared with material with carbon element, and the specific capacity of silicon is high, and its theoretical capacity is up to 4200mAh/g.
But because silicon is in charging and discharging process, violent variation can take place in volume, can destroy the structure of material, causes the cyclical stability of electrode unstable, thereby causes battery failure.And its first irreversible capacity is high, has limited its application as lithium ion battery negative material.
Therefore present many researchs all are devoted to improve and optimize on the performance of silicon-based anode material.
The compound system that the silicon grain outerwrap amorphous carbon layer of employing chemical gaseous phase deposition (CVD) method preparation is arranged at present; The structure and the electric conductivity of silicon materials have been improved; Can restrain the lithium embedding to a certain extent and deviate from the bulk effect in the process, thereby the cycle performance of said material is improved.But the process of CVD method is difficult to control, and uncertain factor is many, therefore is difficult to realize producing in batches.
Summary of the invention
Technical problem to be solved by this invention is: not can manufacture the good silicium cathode material of cycle performance in the prior art.
The silicon composite that is used for the lithium ion battery negative pole that the present invention provides stable cycle performance to produce in batches.
A kind of negative material of lithium ion battery comprises active material and volume buffer, and said active material coats or partly be coated on the surface of the particle of volume buffer, and said active material is a silicon, and said volume buffer is a silicon dioxide.
The present invention also provides a kind of preparation method of above-mentioned negative material, and it comprises: will pass through the powder of pretreated silicon dioxide and the powder vacuum high-temperature sintering of carbonaceous reducing agent; Total weight with silicon dioxide and carbonaceous reducing agent is a benchmark, and the weight of carbonaceous reducing agent accounts for 16.67%-35.8%.
The 3rd purpose of the present invention provides a kind of lithium ion battery; It comprises: battery case, pole piece and electrolyte; Said pole piece and electrolyte sealing are contained in the battery case, and said pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and said positive pole comprises collector and loads on the positive electrode on the collector; Said negative pole comprises collector and loads on the negative material on the collector that said negative material is a negative material provided by the present invention.
Inventor of the present invention finds unexpectedly,, coats or the part coated silica with silicon as coating layer with active material silicon, can effectively suppress volumetric expansion, increases cycle performance.Inventor of the present invention thinks, coats silicon at silica surface, because silicon is coating layer; And coating thickness is less; So lithium ion can embed in the active material silicon easily, and at the surperficial negative material that coats other materials of pure silicon, lithium ion reacts with the surface of its particle easily; And the reacting phase of granule interior causes specific capacity low to difficulty.The inventor infers: because the present invention makes with the particle reduction; Silicon in most of negative material is not the surface that is coated on silicon dioxide fully; But in the zonal coating of silica surface, form discontinuous coating band, longitudinal dilatation and lateral expansion in the time of the silicon change in volume can effectively being suppressed like this; Thereby the powder of detached of effectively avoiding the silicon volumetric expansion to bring, the cycle performance of raising battery.
Negative material powder of detached problem provided by the present invention is obviously improved, thereby has effectively improved the cycle performance of battery.And the specific capacity of negative material provided by the present invention is higher relatively.
Description of drawings
Fig. 1 is the sem photograph (2000 times) of the negative material A1 of the embodiment of the invention 1.
Fig. 2 is the XRD figure of the negative material A1 of the embodiment of the invention 1.
Embodiment
A kind of negative material of lithium ion battery comprises active material and volume buffer, and said active material coats or partly be coated on the surface of the particle of volume buffer, and said active material is a silicon, and said volume buffer is a silicon dioxide.
The average grain diameter of said negative material is 5-20 μ m.
The coating thickness of said active material is 1-8 μ m.
The mass ratio of said active material and said volume buffer is 1: 3-4: 1.So both height ratio capacity can be kept, good cycle can be kept again.
A kind of preparation method of above-mentioned negative material, it comprises: will pass through the powder of pretreated silicon dioxide and the powder vacuum high-temperature sintering of carbonaceous reducing agent; Total weight with silicon dioxide and carbonaceous reducing agent is a benchmark, and the weight of carbonaceous reducing agent accounts for 16.67%-35.8%.
The preparation raw material of said silicon dioxide is meant that natural purity reaches the quartz sand more than 99%, wherein possibly contain Al
3O
2, CaO, Fe
2O
3And P
2O
5Deng impurity.
Said preliminary treatment is meant that it is the superfine silicon dioxide of 5-20 μ m that the silicon dioxide powder breakdown mill is become particle diameter, then superfine silicon dioxide is carried out chemical pickling drying again.
Said pulverizing is ground and is mechanical high-energy ball milling under protection gas atmosphere, and wherein said protection gas is inert gas.
Said chemical pickling can be known in those skilled in the art, and also can be preferably following mode chemical pickling: earlier the superfine silicon dioxide powder is put into chloroazotic acid and stir 3h, to remove heavy metal, metal ion/compound washes with pure water then repeatedly; Superfine silicon dioxide powder after will washing is again put into mass percentage concentration 0.96wt% hydrofluoric acid solution and is stirred 3h, to remove the dephosphorization boride.Wash repeatedly with pure water then, remove chemistry acid.
Said chemical pickling can also comprise that the SiO 2 powder with the process chemical pickling utilizes centrifuge dewatering, and oven drying makes its water content＜1%.
The material of said carbonaceous reducing agent is preferably one or more in coke, native graphite, Delanium and the carbonaceous mesophase spherules; Coke more preferably.
The powder of said carbonaceous reducing agent is meant the above-mentioned material with average grain diameter＜50 μ m, and crushing and classification, shaping and purification process prepare the powder that average grain diameter is 0.1-1 μ m.
Said crushing and classification, shaping and purification process etc. are operating as known in those skilled in the art.
During high temperature sintering, the average grain diameter of said silicon dioxide and said carbonaceous reducing agent ratio is preferably 10: 1-100: 1.
Said high temperature sintering is meant that in sintering furnace following reaction: SiO takes place for silicon dioxide and carbonaceous reducing agent under 1000-2000 ℃ the vacuum environment
2+ 2C=Si+2CO ↑.
Heating rate is preferably 1-10 ℃/min.
The time of said high temperature sintering is preferably 1-24h.
Said sintering furnace is conventionally known to one of skill in the art, for example can be various resistance furnace, induction furnace, arc furnace, crucible etc.The preferred corundum crucible of the present invention.
The present invention is through the ratio of carbonaceous reducing agent and silicon dioxide in the control raw material, controls the ratio of silicon in the negative material of generation.Silicon dioxide is excessive among the present invention, and carbonaceous reducing agent is a silicon with the silicon dioxide partial reduction only, and the relative silica dioxide granule of carbonaceous reducing agent particle is less, mixes to guarantee that carbonaceous reducing agent reacts completely and the covered effect of the silicon that produces is better.Method provided by the invention can be used for industrial mass manufacture fully, and preparation technology is simple relatively.
A kind of lithium ion battery; It comprises: battery case, pole piece and electrolyte; Said pole piece and electrolyte sealing are contained in the battery case, and said pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and said positive pole comprises collector and loads on positive electrode and the conductive agent on the collector; Said negative pole comprises collector and loads on negative material and the conductive agent on the collector that said negative material is a negative material provided by the present invention.
In lithium ion battery of the present invention, electrolyte can be nonaqueous electrolytic solution.Said nonaqueous electrolytic solution is the solution that electrolyte lithium salt forms in nonaqueous solvents, can use the nonaqueous electrolytic solution of routine well known by persons skilled in the art.Can be selected from lithium hexafluoro phosphate (LiPF like electrolyte lithium salt
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), hexafluorosilicic acid lithium (LiSiF
6), tetraphenyl lithium borate (LiB (C
6H
5)
4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl
4) and fluorocarbon based sulfonic acid lithium (LiC (SO
2CF
3)
3), LiCH
3SO
3, LiN (SO
2CF
3)
2In one or more.Nonaqueous solvents can be selected from chain acid esters and ring-type acid esters mixed solution, wherein the chain acid esters can be fluorine-containing for dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other, sulfur-bearing or contain in the chain organosilane ester of unsaturated bond one or more.The ring-type acid esters can (γ-BL), sultone and other be fluorine-containing, sulfur-bearing or contain in the ring-type organosilane ester of unsaturated bond one or more for ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton.In said nonaqueous electrolytic solution, the concentration of electrolyte lithium salt is generally the 0.1-2 mol, is preferably the 0.8-1.2 mol.
In lithium rechargeable battery of the present invention, barrier film is arranged between positive pole and the negative pole, has electrical insulation capability and liquid retainability ability.Said barrier film can be selected from and well known to a person skilled in the art various barrier films used in the lithium rechargeable battery, for example polyolefin micro porous polyolefin membrane (PP), polyethylene felt (PE), glass mat or ultra-fine fibre glass paper or PP/PE/PP.Said barrier film also can be a polyimide film.Said polyimide film can be polyimide film known in those skilled in the art, and preferably its porosity is 20%-55%, and average pore diameter is the 30-120 nanometer.
In lithium rechargeable battery of the present invention, positive electrode active materials can adopt the positive electrode active materials of various routines, like LiFePO4, Li
3V
2(PO
4)
3, LiMn
2O
4, LiMnO
2, LiNiO
2, LiCoO
2, LiVPO
4F and LiFeO
2In one or more.In order significantly to improve said positive electrode active materials performance, said positive electrode active materials is preferably LiFePO4, LiCoO
2, LiVPO
4Among the F one or more.
Wherein, said conductive agent is known in those skilled in the art, and conductive agent generally comprises one or more in graphite powder, carbon black, CNT, HV, titanium valve and the copper powder.
Total weight with negative material and conductive agent is a benchmark, and the weight percentage of said conductive agent is 5-30%.
The preparation method of lithium rechargeable battery provided by the invention carries out according to method as well known to those skilled in the art, and in general, this method comprises anodal, negative pole and the barrier film between positive pole and the negative pole formation pole piece of reeling successively; Pole piece is inserted in the battery case, add electrolyte, then sealing; Wherein, Said negative pole comprises collector and loads on the negative active core-shell material on the collector that wherein, said negative active core-shell material is a negative active core-shell material provided by the invention.Wherein, the method for coiling and sealing is that those skilled in the art are known.The consumption of electrolyte is a conventional amount used.
Through concrete embodiment the present invention is done further explanation below.
Embodiment 1
With the quartz sand of purity more than 99%, mechanical high-energy ball milling to 10 μ m makes the superfine silicon dioxide powder in argon gas atmosphere.
Again the superfine silicon dioxide powder is put into chloroazotic acid and stir 3h, filter the back and wash repeatedly with pure water; Put into mass percentage concentration 0.96wt% hydrofluoric acid again and stir 3h, filter the back and wash repeatedly with pure water; Put into centrifuge then and dewater,, make its water content＜1% at 100 ℃ of oven drying 5h.Process through pretreated SiO 2 powder.
With coke blacking mechanical high-energy ball milling in argon gas atmosphere of average grain diameter＜50 μ m, broken classification prepares the carbonaceous reducing agent that granularity is 0.5 μ m.
360 grams are mixed through pretreated SiO 2 powder and 120 gram carbonaceous reducing agents, fully stir 12h, make it to mix.Send into then under 1000 ℃ the vacuum environment and react, insulation 3h drops to room temperature then, promptly makes negative material A1.
From the sem photograph of Fig. 1, the particle diameter that can find out A1 is roughly about 10 μ m.
From the XRD figure of Fig. 2, can find out: through contrasting with standard diagram, Si can be confirmed to contain at the peak of 28.36,47.23,56.04,69.04,76.32 degree in 2 θ angles; SiO can be confirmed to contain at the peak of 11.92,18.91,21.74,23.35,24.22,50.79 degree in 2 θ angles
2
Embodiment 2
Different is that 420 grams are mixed through pretreated SiO 2 powders and 120 gram carbonaceous reducing agents with embodiment 1.Make negative material A2.
Embodiment 3
Different is that 360 grams are mixed through pretreated SiO 2 powders and 80 gram carbonaceous reducing agents with embodiment 1.Make negative material A3.
Embodiment 4
Different is with embodiment 1, and the average grain diameter of said silicon dioxide is 10 μ m, and the average grain diameter of said carbonaceous reducing agent is 0.1 μ m.Make negative material A4.
Embodiment 5
Different is with embodiment 1, and the average grain diameter of said silicon dioxide is 10 μ m, and the average grain diameter of said carbonaceous reducing agent is 1 μ m.Make negative material A5.
Embodiment 6
(1) preparation of positive pole
With 8.8Kg N-methyl pyrrolidone (NMP), 1Kg acetylene black and 0.2Kg polyvinylidene fluoride (PVDF) powder, stir and be mixed with the acetylene black wash in 5 minutes.
Get the above-mentioned acetylene black slurry for preparing of 2Kg, add 3KgN-methyl pyrrolidone (NMP), 10Kg cobalt acid lithium (the auspicious auspicious company in Hunan produces particle diameter 8 μ m), 0.3Kg polyvinylidene fluoride (PVDF), stir and promptly get battery anode active material after 20 minutes.
Above-mentioned anode active material of lithium ion battery is coated on the aluminum foil current collector that thickness is 20 μ m, and after drying, roll-in and the cut-parts, making length is that 400mm, width are that 44mm, thickness are the positive plate of 0.15mm.
(2) preparation of negative pole
100Kg negative material A1,10kg conductive agent carbon black, 3Kg adhesive butadiene-styrene latex (SBR), 3Kg carboxymethyl cellulose (CMC) are joined in the 50Kg water, in mixer, stir then and form cathode size stable, homogeneous.This slurry is coated on the Copper Foil that thickness is 20 μ m equably, through 120 ℃ of oven dry, roll-in and cut-parts, is that 410mm, width are that 45mm, thickness are the negative plate of 0.18mm thereby make length.
(3) assembling of battery
The positive plate that (1) is obtained, negative plate and the PP/PE/PP barrier film that (2) obtain stack gradually the electrode group that is wound into scroll; The electrode group that obtains is put into the battery case of an end opening; (solvent is an ethylene carbonate: diethyl carbonate=1: 1 (volume ratio) to inject electrolyte 3 grams; LiPF6 concentration be 1 rub/liter), process lithium ion battery F1 after the sealing No. 053450.
Embodiment 7
Different is that negative material is A2, processes lithium ion battery F2 with embodiment 4.
Embodiment 8
Different is that negative material is A3, processes lithium ion battery F3 with embodiment 4.
Embodiment 9
Different is that negative material is A4, processes lithium ion battery F4 with embodiment 4.
Different is that negative material is A5, processes lithium ion battery F5 with embodiment 4.
Comparative Examples 1
Different is that negative material is a pure silicon, processes lithium ion battery H1 with embodiment 4.Performance test
The specific capacity test:
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 electrolyte, and the A1-A5 and pure silicon, conductive carbon black and the Kynoar that are made by the foregoing description 1-5 and Comparative Examples 1 with 0.125 gram are positive electrode with 70: 10: 20 mixture of weight ratio, process button cell S1-S5 and J1.
Battery S1-S5 shelved change into to 0.2 volt of voltage with 0.2 milliampere of electric current after 60 minutes; Then respectively with 1 milliampere, 0.9 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, 0.4 milliampere, 0.3 milliampere, 0.2 milliampere, 0.1 milliampere, 0.09 milliampere, 0.08 milliampere, 0.07 milliampere, 0.06 milliampere, 0.05 milliampere constant current discharge to 0.005 volt; Shelve after 30 minutes with 0.5 milliampere of electric current constant current charge; Record charges to cell voltage and reaches 2.5 volts time; According to normal capacity (MAH)=charging current (milliampere) * charging interval of battery (hour) normal capacity of counting cell, normal capacity promptly gets the electrochemical specific capacity of GND active material (A1-A5 and J1) divided by the weight of the negative active core-shell material (A1-A5 and J1) of battery, the result is as shown in table 1.
The cycle performance test:
Under the room temperature, with battery (F1-F5 and H1) with 1C electric current constant current charge to 4.2V, lower voltage limit 2V, cut-off current 0.02C; And then with battery with 1C electric current constant-current discharge to 3.V.Repeat above step 150 time, obtain the capacity of 150 circulation backs of battery normal temperature 1C current discharge, battery capacity conservation rate after the computation cycles to 3.0V.The result sees table 2.
Table 1
| Negative material | A1 | A2 | A3 | A4 | A5 | Silicon |
| Specific capacity (mAh/g) | 2052 | 1698 | 1326 | 2104 | 1985 | 2997 |
Table 2
| Battery | F1 | F2 | F3 | F4 | F5 | H1 |
| 150 circulation volume conservation rates (%) | 71.2 | 81.7 | ?89.6 | 74.7 | ?69.1 | 0 |
Annotate: H1 capability retention after circulation 35 times is 0.
Can find out from table 1 and table 2,,, still keep higher specific capacity in art technology people acceptable scope though specific capacity of the present invention is lower than the specific capacity of pure silicon.But 150 circulation volume conservation rates of battery of the present invention can reach about 70%, have well solved the problem of the cycle performance difference of silica-base material.
Claims (9)
1. the negative material of a lithium ion battery comprises active material and volume buffer, and said active material coats or partly be coated on the surface of the particle of volume buffer, and said active material is a silicon, and said volume buffer is a silicon dioxide; The average grain diameter of said negative material is 5-20 μ m; The coating thickness of said active material is 1-8 μ m; The mass ratio of said active material and said volume buffer is 1: 3-4: 1.
2. the preparation method of the described negative material of claim 1, it comprises: will pass through the powder of pretreated silicon dioxide and the powder vacuum high-temperature sintering of carbonaceous reducing agent; Total weight with silicon dioxide and carbonaceous reducing agent is a benchmark, and the weight of carbonaceous reducing agent accounts for 16.67%-35.8%.
3. preparation method according to claim 2 is characterized in that: said preliminary treatment is meant that it is the superfine silicon dioxide of 5-20 μ m that the silicon dioxide powder breakdown mill is become average grain diameter, carries out chemical pickling with superfine silicon dioxide then.
4. preparation method according to claim 2 is characterized in that: said carbonaceous reducing agent comprises one or more in coke, native graphite, Delanium and the carbonaceous mesophase spherules.
5. preparation method according to claim 4 is characterized in that: said carbonaceous reducing agent is a coke.
6. preparation method according to claim 2 is characterized in that: the average grain diameter of said carbonaceous reducing agent is 0.1-1 μ m.
7. preparation method according to claim 2 is characterized in that: the average grain diameter ratio of said silicon dioxide and said carbonaceous reducing agent is 10: 1-100: 1.
8. preparation method according to claim 2 is characterized in that: the temperature of said high temperature sintering is 1000-2000 ℃, and heating rate is 1-10 ℃/min, and the high temperature sintering time is 1-24h.
9. lithium rechargeable battery; It comprises: battery case, pole piece and electrolyte; Said pole piece and electrolyte sealing are contained in the battery case, and said pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and said positive pole comprises collector and loads on the positive electrode on the collector; Said negative pole comprises collector and loads on the negative material on the collector that said negative material is the described negative material of claim 1.
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| JP5621867B2 (en) * | 2012-03-27 | 2014-11-12 | Tdk株式会社 | Lithium ion secondary battery |
| CN102820451A (en) * | 2012-07-23 | 2012-12-12 | 深圳市海太阳实业有限公司 | Negative electrode pole piece and preparation method thereof, and lithium ion battery and preparation method thereof |
| JP5967024B2 (en) * | 2013-06-20 | 2016-08-10 | 信越化学工業株式会社 | Non-aqueous electrolyte secondary battery active material, negative electrode molded body, and non-aqueous electrolyte secondary battery |
| CN105406050B (en) * | 2015-12-31 | 2018-11-02 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of comprehensive silicon negative material, preparation method and purposes |
| CN106328909B (en) * | 2016-11-18 | 2020-01-24 | 深圳市贝特瑞新能源材料股份有限公司 | Nano silicon dioxide-silicon-based composite material, preparation method and lithium ion battery containing composite material |
| JP6941302B2 (en) * | 2017-01-11 | 2021-09-29 | Jnc株式会社 | Polysilsesquioxane-coated silicon nanoparticles or their fired product and its manufacturing method, negative electrode active material for lithium ion batteries, negative electrode for lithium ion batteries, and lithium ion batteries |
| JP6969483B2 (en) * | 2018-04-09 | 2021-11-24 | トヨタ自動車株式会社 | Lithium-ion secondary battery and its manufacturing method |
| CN110364662B (en) * | 2018-04-11 | 2022-07-05 | 宁德新能源科技有限公司 | Separator and electrochemical device |
| CN113176300A (en) * | 2021-04-25 | 2021-07-27 | 南方科技大学 | Photoelectric humidity sensor based on artificial opal humidity-sensitive material |
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| CN1428880A (en) * | 2001-12-26 | 2003-07-09 | 信越化学工业株式会社 | Conductive silicon oxide powder, its mfg. method and negative electrode material of nonaqueous electrolyte secodary battery |
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