CN101585528A - The preparation method of lithium ion battery negative material and product thereof - Google Patents
The preparation method of lithium ion battery negative material and product thereof Download PDFInfo
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- CN101585528A CN101585528A CNA2008101001044A CN200810100104A CN101585528A CN 101585528 A CN101585528 A CN 101585528A CN A2008101001044 A CNA2008101001044 A CN A2008101001044A CN 200810100104 A CN200810100104 A CN 200810100104A CN 101585528 A CN101585528 A CN 101585528A
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Abstract
A kind of preparation method of lithium ion battery negative material and product thereof, this preparation method comprises: preparation one is mixed with a modification liquid of carbon back material, make it form carbon back material to make this carbon back material whereby once modification through a combination treatment, be placed on afterwards under the non-oxidizing gas atmosphere carrying out a drying treatment, and obtain this lithium ion battery negative material; This modification liquid is to include first component that a polar solvent and has stannous fluoboric acid, fluoroboric acid, thiocarbamide, or one second component, it has tin protochloride, Tripotassium Citrate, and following at least one alkaline agent: potassium hydroxide, lithium hydroxide, with sodium hydroxide; The product of the inventive method prepares that speed is fast, safe, step is simple, is lithium ion battery negative material between 0.8～1.2 and the present invention also provides about a kind of atomic quantity ratio that it adheres to the sulphur of material and tin.
Description
Technical field
The present invention relates to a kind of preparation method of battery material, particularly a kind of can be in order to preparation method as lithium ion battery negative material.The present invention also relates to product about this preparation method.
Background technology
It is little that lithium ion battery (Lithium ion battery) has a volume, and long-time the use down still keep advantages such as high reserve of electricity and high discharge capacity, thereby be used in widely in the equipment such as communication, electronics." carbon back material " (carbonaceous material) considers based on its security and cost, becomes the raw material main flow of lithium ion battery negative material already; And various be the lithium ion battery negative material of raw material with the carbon back material, and relevant preparation method also is developed gradually.
Paper Journal of Power Sources, the technology that 102 (2001) 60-67. are disclosed is permeate water hot hydrogen reduction method (hydrothermal hydrogen reductionmethod; It is under 150 ℃, in a nickel ammonium sulfate (Ni (NH who is mixed with the carbon back material
4)
nSO
4) feed high pressure hydrogen in the aqueous solution) preparing lithium ion battery negative material, it includes this carbon back material and modification nickel metal thereon; But this method is at high temperature to use high pressure hydrogen, the operational danger height.
Paper Electrochemistry Communications, 5 (2003) 657. technology that disclosed are that (Mesocarbon Microbeads, MCMB) adding is dissolved with SnCl with Jie's phase carbon ball
2, NiCl
2, with Trisodium Citrate (sodium citrate, Na
3C
6H
5O
7) the aqueous solution in, again it is imposed ultrasound concussion, afterwards one hour then slowly with NaBH
4Be incorporated in this solution and stir this solution simultaneously,, at last after filtration, diafiltration, and finish whole preparation procedure under 5 hours the steps such as drying treatment so that tin-nickel alloy is deposited on the surface of MCMB; This method has the complicated (NaBH particularly of schedule of operation as from the foregoing
4Poor stability, easily and air reaction), shortcoming such as the operating time is tediously long.
Paper Carbon, 41 (2003) 959. technology that disclosed are to containing SnCl
2, SbCl
3, CNT (carbon nano-tube) (carbon nanotube) water in suspension liquid, add in order to KBH with the addition manner that is divided into repeatedly as metallic reducing agent
4, then after filtration, step such as washing and oven dry and obtain a lithium ion battery negative material, it includes this CNT (carbon nano-tube) and modification tin metal and antimony metal thereon; KBH wherein
4Add because of need are divided into repeatedly, also make this method for making trouble that on operation steps, seems.Above-described two kinds of methods are applicable to a small amount of preparation of for example carrying out in the laboratory, and are unfavorable for that industrial community carries out the mass production processing procedure.
In addition, paper Electrochimica Acta, 50 (2004) 517. preparation methods that proposed, then be with 55 ℃ be service temperature, contain SnCl and MCMB is suspended in
2, NaOH, Na
3C
6H
5O
7, NaH
2PO
2Modification liquid in, then after filtration, step such as washing and oven dry and obtain a lithium ion battery negative material, it includes MCMB and modification in its lip-deep tin phosphorus compound; Nearly four kinds of the employed chemical substances of this method, short by the battery life that this lithium ion battery negative material is made on the other hand, electrical capacity is not high yet, is unfavorable for using.
Summary of the invention
Production line is planned, laid to a purpose of the present invention promptly providing a kind of kind safe, easy and simple to handle, spent material few, and help industrial community at low cost, makes the preparation method of lithium ion battery negative material whereby in a large number.The preparation method of lithium ion battery negative material of the present invention, comprise: preparation one is mixed with a modification liquid of carbon back material, make it form carbon back material to make this carbon back material whereby once modification through a combination treatment, be placed on a non-oxidizing gas atmosphere afterwards and get off to carry out a drying treatment, and obtain this lithium ion battery negative material; Wherein, this modification liquid includes a polar solvent and one first component or one second component, and this first component has stannous fluoboric acid, fluoroboric acid, and thiocarbamide, and this second component then has tin protochloride, Tripotassium Citrate (potassium citrate, K
3[C
3H
5O (COO)
3]), and following at least one alkaline agent: potassium hydroxide, lithium hydroxide, with sodium hydroxide.
Above-mentioned exsiccant " through the carbon back material of modification " can make really and utilize its prepared lithium ion battery that goes out to carry out normal operation, thereby can be in order to as lithium ion battery negative material.
The preparation method of lithium ion battery negative material of the present invention, in every liter modification liquid, the incorporation of this carbon back material is between 0.1 gram～600 grams; This combination treatment is to carry out to the ebullient temperature range at 60 ℃; This non-oxidizing gas atmosphere more includes the following hydrogen of 5vol%, and this drying treatment is not to be higher than 10
-2The holder atmospheric pressure value under, carry out in 20 ℃～150 ℃ temperature ranges.
The preparation method of lithium ion battery negative material of the present invention, in every liter modification liquid, the incorporation of this carbon back material is between 0.1 gram～450 grams; This combination treatment is to carry out in 60 ℃～90 ℃ temperature range.
The preparation method of lithium ion battery negative material of the present invention, this carbon back material is selected certainly in intermediate phase Graphite Powder 99, Jie's phase carbon ball, ball-type carbon material, synthetic graphite, natural graphite, CNT (carbon nano-tube), hard carbon, or an above-mentioned combination; This polar solvent is selected certainly in water, alcohols, aldehydes, ketone, or an above-mentioned combination; This non-oxidizing gas atmosphere is nitrogen, rare gas element, carbonic acid gas, or an above-mentioned combination.
The preparation method of lithium ion battery negative material of the present invention, this modification liquid includes this first component, and in every liter modification liquid, this modification liquid is dissolved with 0.01 mole～2 moles stannous fluoboric acid, 0.01 mole～2 moles fluoroboric acid, and 0.01 mole～5 moles thiocarbamide.
The preparation method of lithium ion battery negative material of the present invention, in every liter modification liquid, this modification liquid is dissolved with 0.075 mole～1.25 moles stannous fluoboric acid, 0.1 mole～1 mole fluoroboric acid, and 0.5 mole～4 moles thiocarbamide.
The preparation method of lithium ion battery negative material of the present invention, this modification liquid includes this second component, and modification liquid in every liter, this modification liquid is dissolved with 0.005 mole～3 moles tin protochloride, 0.005 mole～8 moles alkaline agent, and 0.005 mole～3 moles Tripotassium Citrate.
The preparation method of lithium ion battery negative material of the present invention, this modification liquid is dissolved with 0.05 mole～2 moles tin protochloride, 0.5 mole～2.5 moles alkaline agent, and 0.01 mole～1 mole Tripotassium Citrate.
A kind of lithium ion battery negative material includes a carbon back material, and one attached to the material that adheres on this carbon base material surface, this adheres to material and is discontinuously arranged particulate state, and the atomic quantity ratio of its sulphur and tin is between 0.8～1.2.
Lithium ion battery negative material of the present invention, this atomic quantity ratio that adheres to sulphur and tin in the material is between 0.8667～1.0588.
Lithium ion battery negative material of the present invention, this size range of adhering to material is between 3nm～200nm.
Lithium ion battery negative material of the present invention, this size range of adhering to material is between 3nm～100nm.
Lithium ion battery negative material of the present invention, it is to make with preparation method of the present invention.
Preparation method's of the present invention beneficial effect is: it need not use a large amount of hydrogen, does not therefore have the misgivings of security; In addition its when carrying out, the material variety that must use few, need be in this is mixed with the modification liquid of carbon back material, not adding unclassified stores more in addition under the stage of combination treatment yet, case must gradation and routinely add NaBH before the right aforesaid major part
4, KBH
4, the security of the inventive method is higher apparently, and more easy in the operation.
In addition with regard to composition, lithium ion battery negative material of the present invention includes a carbon back material, and one attached to the material that adheres on this carbon base material surface.Under the application applicant's revision test repeatedly, find when preparation method of the present invention be when carrying out with the modification liquid that includes this first component, according to energy dispersive spectroscopy instrument (Energy DispersiveSpectrometer, EDS) analyze conclusion, this adheres to S in the material and the atomic quantity ratio of Sn approaches 1, and this result does not see in this area; The applicant infers that this adheres to material and should be SnS.
Therefore, another object of the present invention is that a kind of lithium ion battery negative material is being provided, and it includes a carbon back material, and one attached to the material that adheres on this carbon base material surface, and this adheres to, and the atomic quantity ratio of sulphur and tin is between 0.8～1.2 in the material; And this novel lithium ion battery negative material can see through the above-mentioned modification liquid that contains first component, makes by preparation method of the present invention.
Description of drawings
Fig. 1 is SEM figure, a NG carbon dust that does not pass through any processing is described under 40000 times enlargement ratio, the kenel that its surface presented;
Fig. 2 is SEM figure, the lithium cell cathode material that is obtained by embodiment 1 is described under 40000 times enlargement ratio, the kenel that its surface presented;
Fig. 3 is TEM figure, illustrate that the lithium cell cathode material surface that is obtained by embodiment 2 amplifying the kenel that is presented under the observation;
Fig. 4 is an element analysis chart, is the EDS analytical results that adheres to material on embodiment 1 lithium cell cathode material; Its C, O, S, the plain shared weight percent of Sn quaternary are respectively 91.09%, 3.36%, 1.11%, 4.45%, and shared atomicity per-cent is respectively 96.42%, 2.67%, 0.44%, 0.48%;
Fig. 5 is a cycle life figure, and the charge/discharge test result of application examples 1～5 and comparative example is described;
Fig. 6 is SEM figure, the lithium cell cathode material that is obtained by embodiment 6 is described under 80000 times enlargement ratio, the kenel that its surface presented;
Fig. 7 is an element analysis chart, is the EDS analytical results that adheres to material on embodiment 6 lithium cell cathode materials; Its C, O, the shared weight percent of Sn element are respectively 52.09%, 26.31%, 21.60%, and shared atomicity per-cent is respectively 70.37%, 26.68%, 2.95%;
Fig. 8 is a cycle life figure, and the charge/discharge test result of application examples 6～10 and comparative example is described;
Fig. 9 is a cycle life figure, and the charge/discharge test result of application examples 11～19 and comparative example is described.
Embodiment
The preparation method's of lithium ion battery negative material of the present invention elementary operation important document is set forth in, and is then as follows with regard to preferable, the better embodiment of each operation important document.
The consumption of employed each material of the inventive method basically and unrestricted, below relevant for the related description of each material consumption, be to be that benchmark calculates with every liter modification liquid.
With regard to this carbon back material, as long as mix, but incorporation when high more total surface area also just big more, relatively make its formed material that adheres on per surface area understand less naturally.Preferably its incorporation is between 0.1 gram～600 grams, more preferably is between 0.1 gram～450 grams.In addition, the kind of this carbon back material is not limited yet, but the carbon back material with high surface area is used in suggestion, and for example meal is attached to this carbon base material surface in order to adhering to material.Preferably this carbon back material is selected certainly in intermediate phase Graphite Powder 99 (mesophase graphite powder, MGP), MCMB, ball-type carbon material (carboncapsule), synthetic graphite (artificial graphite), natural graphite (naturalgraphite), CNT (carbon nano-tube), hard carbon (hard carbon), an or above-mentioned combination.In model shown in following examples, this carbon back material with respect to the incorporation of every liter of modification liquid be 250 grams to 416 grams, selected kind is powdered natural graphite (abbreviating " NG carbon dust " as).
Other it should be noted that the inventive method also can be used originally and promptly have appendiculate carbon back material on its surface, is for example demonstrated with lower section embodiment; And such modus operandi also is similar to carbon back material of its surface being gone up no any dirt settling, by repetitive operation the inventive method by gradation modification.The applicant infers, when controlling the employed modification liquid of each time composition further, can be in the carbon base material surface of last acquisition, have the multiple material that adheres to, and the application applicant has also passed through following examples, confirm that such the inventive method product can make follow-up prepared battery normally operate, and be able to as lithium ion battery negative material.
Desire is implemented visual its demand of personage of the inventive method and is selected accordingly to use to include this first component, or the modification liquid of this second component, as long as and the polar solvent that is adopted in principle can be with first component, or each material dissolution in second component gets final product.Therefore, this polar solvent can be water, alcohols, aldehydes, ketone, or an above-mentioned combination.Preferably, alcohols is methyl alcohol (methanol), ethanol (ethanol), propyl alcohol (propanol), butanols (butanol), amylalcohol (pentanol), Virahol (isopropanol); Ketone is acetone (acetone), butanone (methylethyl ketone), N-methyl-2-Pyrrolidine ketone (N-Methyl-2-Pyrrolidone, NMP; C
5H
9NO); Aldehydes then is a butyraldehyde (butyraldehyde).In model shown in following examples, this polar solvent is a water.
The consumption upper limit of each material is to reach capacity to the modification liquid concentration of joining in this first component or second component.With regard to this modification liquid is the content that the situation that is dissolved with first component is considered each material, and stannous fluoboric acid is preferably and is dissolved with 0.01 mole～2 moles, more preferably is to be dissolved with 0.075 mole～1.25 moles; Fluoroboric acid is preferably and is dissolved with 0.01 mole～2 moles, more preferably is to be dissolved with 0.1 mole～1 mole; Thiocarbamide is preferably and is dissolved with 0.01 mole～5 moles, more preferably then is to be dissolved with 0.5 mole～4 moles.In model shown in following examples, contain the modification liquid of first component, be to be dissolved with 0.15 mole～0.75 mole stannous fluoboric acid, 0.21 mole～0.273 mole fluoroboric acid, and 1.39 moles～2.78 moles thiocarbamide.
Be the content that the situation that is dissolved with second component is considered each material with this modification liquid in addition, tin protochloride is preferably and is dissolved with 0.005 mole～3 moles, more preferably is to be dissolved with 0.05 mole～2 moles; Alkaline agent is preferably and is dissolved with 0.005 mole～8 moles, more preferably is to be dissolved with 0.5 mole～2.5 moles; Tripotassium Citrate is preferably and is dissolved with 0.005 mole～3 moles, more preferably is to be dissolved with 0.01 mole～1 mole Tripotassium Citrate.In model shown in following examples, contain the modification liquid of second component, be to be dissolved with 0.075 mole～0.18 mole tin protochloride, 0.9 mole～1.95 moles alkaline agent (KOH or LiOH), and 0.1 mole～0.2 mole Tripotassium Citrate.
This combination treatment can be undertaken by modes such as stirring, ultrasonic oscillations, with so that each material in carbon back material and this modification liquid is in contact with one another as best one can, adheres to material and is formed on purpose on this carbon base material surface and reach to impel.Promote the temperature of combination treatment, feed electric current or the like operation skill when combination treatment in this modification liquid, all help reaching this purpose, preferably, this combination treatment is to carry out to the ebullient temperature range at 60 ℃; And operation for the benefit of more preferably is to carry out in 60 ℃～100 ℃ temperature range.In model shown in following examples, this combination treatment is to carry out in 70 ℃ to 95 ℃ temperature range.
Find on the practice if only with the execution time length of combination treatment be unique change because of the time, long (can make this carbon base material surface modification that the more material that adheres to is arranged) of time might not make the follow-up battery of making have more powerful effect or long work-ing life, so the preferable execution time of combination treatment is to look each case and discuss.In model shown in following examples, the time of combination treatment is not wait to 3 hours in 30 seconds.
Form via this combination treatment after modification carbon back material takes out in this modification liquid, be dried by this drying treatment; The temperature of this drying treatment, pressure do not have basic restriction, as long as but can make be able to through modification carbon back material dry.Preferably, this drying treatment is in 20 ℃～150 ℃ temperature ranges, is not higher than 10
-2Carry out under the atmospheric pressure value of holder.
The employed non-oxidizing gas atmosphere of this drying treatment is to desire to avoid this oxidized in this drying treatment process through modification carbon back material, have influence on the effect or the work-ing life of the follow-up lithium ion battery of making, so this non-oxidizing gas atmosphere basically only otherwise containing any gas (for example oxygen) with oxidation capacity gets final product, preferably, this non-oxidizing gas atmosphere is nitrogen, rare gas element, carbonic acid gas, or an above-mentioned combination.On the other hand, can also include in this non-oxidizing gas atmosphere in order to a little hydrogen as reductive agent, for considering security, the content of suggestion hydrogen is below 5vol%.In model shown in following examples, be at 90 ℃, 10
-2Carry out drying treatment in the nitrogen of holder.
The inventive method lithium ion cell prepared negative material includes a carbon back material, and one attached to the material that adheres on this carbon base material surface, it is discontinuously arranged particulate state; This size range of adhering to material is preferably between 3nm～200nm, and more preferably then between 3nm～100nm, and in model shown in following examples, this size range of adhering to material then is between 10nm～100nm.
In addition, if when carrying out the inventive method with the modification liquid that only contains first component, this atomic quantity ratio that adheres to sulphur and tin in the material is basically between 0.8～1.2; In model shown in following examples, then between 0.8667～1.0588.
Below the embodiment and the effect of each purpose of the present invention will be described with embodiment/application examples and conjunction with figs..Employed chemical of these embodiment/application examples and equipment are as follows.It is noted that these embodiment/application examples only illustrate in order to conduct, and should not be interpreted as restriction of the invention process.Temperature, pressure unless otherwise noted, the then execution of embodiment/application examples or preparation, and follow-up every test and evaluation all are to carry out under normal temperature, non-pressurized environment.
[embodiment]
＜chemical 〉
1.NG carbon dust: provide by steel carbon element chemical company in the Taiwan.
2. stannous fluoboric acid (Sn (BF
4)
2): made by Belgian Acros company, purity is 50%.
3. fluoroboric acid (HBF
4): made by Spain Panreac company, purity is 35%.
4. thiocarbamide ((NH
2)
2CS): made by Japanese Wako company, purity is 99%.
5.SnCl
22H
2O: made by Spain Panreac company, purity is 98%.
6.KOH: made by Spain Panreac company, purity is 99%.
7.LiOH: made by Taiwan Merck company, purity is 98%.
8. Tripotassium Citrate (K
3C
6H
5O
7H
2O): made by Spain Panreac company, purity is 99.5%.
＜embodiment 1～5 〉
With the secondary deionized water is solvent, in regular turn with thiocarbamide, fluoroboric acid, stannous fluoboric acid (above three is the material of " first component ") dissolving, to be mixed with the modification liquid that a volume is 600ml; Be warming up to afterwards 80～95 ℃ and add 250 the gram the NG carbon dusts, utilize magnetite to carry out a combination treatment simultaneously with being stirred, the NG carbon dust is modified.
This after the NG of modification carbon dust (it also comprises attached to its lip-deep dirt settling except NG carbon dust originally) leaches, is cleaned for several times with a little secondary deionized water, and moving in one is nitrogen atmosphere again, and atmospheric pressure value is controlled to be 10
-2In the baking oven of holder, under 90 ℃, carry out drying treatment, take out exsiccant through modification NG carbon dust after lasting 180 minutes.
The operations condition of embodiment 1～5 is as shown in table 1; The consumption of each material in first component means " every liter of mole number that modification liquid is dissolved with ", and directly represents with volumetric molar concentration (M).
Table 1
The sem analysis of embodiment 1～5 product
Utilize FEI Co. to make, model is one scan formula electron microscope/energy dispersive spectroscopy instrument (scanning electron microscope/energydispersive spectrometer of Quanta 400F, be designated hereinafter simply as " SEM/EDS "), under specific enlargement ratio, observe embodiment 1～5 product (exsiccant is through modification NG carbon dust) surface.
One do not pass through any processing NG carbon dust (comparative example) surface the sem analysis result as shown in Figure 1, under identical enlargement ratio, the surface morphology of the dry NG carbon dust that embodiment 1 is obtained is as shown in Figure 2 in addition.Difference between this two figure has obviously confirmed material that embodiment 1 obtained except including the NG carbon dust as Fig. 1, also comprises to be attached to its surperficial material (below be called " dirt settling ").Observe through amplifying, the size range of knowing this dirt settling is between 10nm～100nm, and wherein, the size range of most of dirt settling is between 10nm～40nm.
In addition, (transmission electronmicrograph TEM) observes the surface of the dry NG carbon dust that embodiment 2 obtained, and then can see its size even little dirt settling to 2nm is arranged with transmission electron microscope as illustrated in fig. 3.
The EDS of embodiment 1～5 product analyzes
Utilize the EDS function in the above-mentioned SEM/EDS instrument further, come dirt settling to embodiment 1～5 to impose EDS and analyze, to know element that they are contained and the quantitative proportion between each element; Operating parameters is as follows: the scanning of a surface region area is 3.5 μ m * 3.5 μ m, and the electron beam intensity that uses is 25KeV.
EDS analytical results such as Fig. 4 of embodiment 1 show carbon, oxygen, sulphur, four kinds of elements of tin and are detected, and wherein S is 44: 48 with the atom number ratio of Sn; The dirt settling EDS analytical results of embodiment 2～5 also result with embodiment 1 is very similar, and four kinds of above-mentioned elements are also all recorded, and difference only is that each atoms of elements number ratio is slightly different, but S is still extremely identical with the atom number of Sn.
Now the shared number ratio of each atom that the EDS analytical results of embodiment 1～5 dirt settling is known, put in order in following table 2:
Table 2
As shown in Table 2, it is almost equal that these adhere in the material atom number of S and Sn, thereby infer that these adhere to material might be SnS.
＜application examples 1～5 〉
The exsiccant of embodiment 1～5 is through modification NG carbon dust, will with an electro-conductive material (carbon black; Made by MMM Carbon (Belgium) company, model is Super-S), a tackiness agent (PVDF; Made by Solef company, model is 6020, and molecular weight is 304,000), and oxalic acid (made by SHOWA company, purity is 99.0%) was according to weight ratio 90: 3: 6.9: 0.1 ratio is doping to a solid constituent, gets the solvent (NMP of the 51wt% of this constituent then; Made by Aldrich company, purity is 99.5%) and this solid constituent uniform mixing, and form a mashed prod; This mashed prod is coated in the form of sheets a current collection material (Copper Foil; Made by Nippon foil company, thickness is 15 μ m) on, pressurize again after drying, cut, and form this cathode pole piece.
Afterwards, for each cathode pole piece prepares respectively as follow-up described battery component and electrolytic solution, and be below the 10ppm and be provided with the glove box of a battery cap machine (great poly-Industrial Co., Ltd. make) (Unilab Mbraum company makes in its water oxygen level, model is Proj-4189) in assemble, come capping (to guarantee its closure) with this battery cap machine in addition, and obtain a Coin shape lithium ion battery (being application examples 1～5) to be tested respectively; Comparative example (the NG carbon dust with not process modification is a lithium electronics negative material) then is in an identical manner, makes a lithium-ion secondary cell.
The relevent information of this battery component and electrolytic solution is following-
＜electrolytic solution 〉
1. ionogen: LiPF
6, to make by Ferro company, purity is 99.0%.
2. solvent: equiponderant NSC 11801 and methylcarbonate, all to make by German Merck company, purity is all 99%.
＜battery component 〉
1. upper shell cover and lower cover: great poly-Industrial Co., Ltd. makes by Taiwan, and model is 2032.
2. compression spring, stainless steel disk: great poly-Industrial Co., Ltd. makes by Taiwan.
3. barrier film: made by Celgard company, model is Celgard 2300.
4. anode pole piece: the lithium paper tinsel, make by FMC Corp., be purity 99.9%, the disk that diameter is 1.65 centimeters.
＜effect test 〉
[charge/discharge test]
By a charge-discharge test machine (good excellent scientific ﹠ technical corporation makes by Taiwan, and model is BAT-700S), with 0.326mAcm
-2Electric current (0.1C) carries out constant-current charge to each battery of application examples 1～5 and comparative example, shows that this battery circuit voltage arrives till the 0.01V, obtains the charging capacitor numerical quantity first time of this battery to the instrument; After 10 minutes, with 0.326mAcm
-2Electric current, each battery is carried out till constant-current discharge to circuit voltage arrives 2.0V, obtain their the discharge capacity numerical quantity first time, then repeatedly repeat above-mentioned charging, discharge step, and measured discharge capacity numerical quantity when synchronously each time being discharged, arrangement is result as shown in Figure 5, therefrom also can understand each battery under the situation of multiple charge/discharge, the development trend of its electrical capacity; And the application examples/comparative example that each conventional letter corresponded among Fig. 5 then is illustrated in the following table 3:
Table 3
The presentation of results of Fig. 5, the lithium ion battery that the exsiccant that is obtained by embodiment 1～5 makes through modification NG carbon dust (being application examples 1～5), but normal operation really, thereby the product that proof embodiment 1～5 is made can be used as lithium ion battery negative material; Further, after only going through 10 times charge and discharge repeatedly, the electrical capacity of application examples 1～5 promptly all is higher than comparative example significantly, live through the number of times that charges and discharge more repeatedly, the electrical capacity difference amplitude of comparative example and application examples 1～5 is just big more, so relatively, grown many work-ing life of obvious application examples 1～5 than comparative example, thereby also provable embodiment 1～5 can prepare the lithium ion battery negative material with better quality really.
Other looks back table 1, embodiment 1～5 only need carry out 30 minutes after its modification liquid prepares, even 30 seconds combination treatment, obviously preparation method's very advantageous on time cost of embodiment 1～5 is made lithium ion battery negative material in a large number and help industrial community.
＜embodiment 6～10 〉
With the secondary deionized water is solvent, with KOH, Tripotassium Citrate, tin protochloride (above three is the material of " second component ") dissolving, is mixed with a modification liquid in regular turn; Be warming up to 75～80 ℃ and add the NG carbon dust afterwards, utilize magnetite to carry out a combination treatment simultaneously with being stirred, last 1.5 hours～do not wait in 3 hours, the NG carbon dust is modified.
This after the NG of modification carbon dust leaches, is cleaned for several times it with secondary deionized water, and the water liquid after cleaning to it is with Ag (NO)
3Do not have when (aq) splashing into till the precipitation generation, will be somebody's turn to do afterwards again in the NG of modification carbon dust immigration one is nitrogen atmosphere, and atmospheric pressure value is controlled to be 10
-2In the baking oven of holder, under 90 ℃, carry out drying treatment, take out exsiccant through modification NG carbon dust after lasting 180 minutes.
The operations condition of embodiment 6～10 is as shown in table 4; The consumption of each material in second component means " every liter of mole number that modification liquid is dissolved with ", and directly represents with volumetric molar concentration (M).
Table 4
The sem analysis of embodiment 6～10 products and EDS analyze
Embodiment 6～10 exsiccant that obtains carries out sem analysis through modification NG carbon dust in aforesaid mode.The surface morphology of embodiment 6 as shown in Figure 6; Obviously the NG carbon dust makes there are some dirt settlings on its surface because of the operating process of embodiment 6 really.The sem analysis result of the product of embodiment 7～10 also is like this.
In addition, the EDS analytical results of the dirt settling of embodiment 6 products then as shown in Figure 7; Be similar to the EDS analytical results of embodiment 1～5 product, the dirt settling of embodiment 7 also has analyzed to carbon, oxygen, sulphur, four kinds of elements of tin, and according to its EDS analytical results, be aided with embodiment 6 employed various materials for considering, the applicant infers that these dirt settlings should be tin protoxide (SnO) and tin.The EDS analytical results of embodiment 7～10 also result with embodiment 6 is very similar, will not repeat.
＜application examples 6～10 〉
The exsiccant that is obtained with embodiment 6～10 carries out the operating method of application examples 1 respectively, and respectively makes a Coin shape lithium ion battery (being application examples 6～10) to be tested through modification NG carbon dust; In addition, also carry out the charge/discharge test that application examples 1 is accepted.
Application examples 6～10 in this test when each time discharged measured discharge capacity numerical quantity, put in order as shown in Figure 8, therefrom also can understand each battery under the situation of multiple charge/discharge, the development trend of its electrical capacity; And the embodiment/comparative example that each conventional letter corresponded among Fig. 8 then is illustrated in the following table 5:
Table 5
The result of Fig. 8 confirms, the lithium ion battery (being application examples 6～10) that makes through the NG of modification carbon dust that is obtained by embodiment 6～10, but normal operation really, thereby the product that proof embodiment 6～10 is made can be used as lithium ion battery negative material; Under charge-discharge test repeatedly, the performance of the electrical capacity of application examples 6～10 also nearly all is better than comparative example in addition, can prepare the lithium ion battery negative material with better quality really so confirm the method for embodiment example 6～10.
＜embodiment 11～19 〉
The modus operandi of embodiment 11～19 is similar with the modus operandi of embodiment 6～10, but employed carbon back material, be that (this pre-treatment is similar embodiment 1～5 a described program to the prior NG carbon dust of having accepted a pre-treatment thereby being modified, but handle without super-dry), therefore before embodiment 11～19 carried out, promptly existing dirt settling existed on this NG carbon dust surface.
This pre-treatment is employed to be 75 gram NG carbon dusts, and the operations condition of this pre-treatment and embodiment 11～19 is as shown in table 6, wherein, and the long-pending 300ml that is all of the modified liquid of all uses; And the consumption of each material in first component and second component is to mean " every liter of mole number that modification liquid is dissolved with ", and directly represents with volumetric molar concentration (M).
Table 6
＜application examples 11～19 〉
The exsiccant that is obtained by embodiment 11～19 carries out the operating method as application examples 1 respectively, and respectively makes a Coin shape lithium ion battery (being application examples 11～19) to be tested through modification NG carbon dust; In addition, also carry out the charge/discharge test that application examples 1 is accepted.
Application examples 11～19 in this test when each time discharged measured discharge capacity numerical quantity, put in order as shown in Figure 9, therefrom also can understand each battery under the situation of multiple charge/discharge, the development trend of its electrical capacity; And the embodiment/comparative example that each conventional letter corresponded among Fig. 9 then is illustrated in the following table 7:
Table 7
The result of Fig. 9 confirms, the lithium ion battery that the carbon back material through modification that is obtained by embodiment 11～19 makes (being application examples 11～19), but normal operation really, thereby the product that proof embodiment 11～19 is made can be used as lithium ion battery negative material.In addition under charge-discharge test repeatedly, the electrical capacity performance of application examples 11～19 also nearly all is better than comparative example, particularly charging and discharging number of times above under 35 times the situation, the electrical capacity difference of these application examples and comparative example is more obvious, and as can be known the longer service life of application examples 11～19 in comparative example; Really can prepare lithium ion battery negative material so confirm the method for embodiment 11～19 with better quality.
The result of comprehensive the foregoing description and application examples, obviously the inventive method really can be by including the modification liquid of this first component or second component, only pass through this combination treatment and drying treatment in regular turn, can take into account and prepare lithium ion battery negative material safely under extra interpolation (particularly each a little and the routinely) unclassified stores not needing; Further, when this modification liquid includes this first component, only need short 30 seconds combination treatment, can make lithium ion battery negative material, so the inventive method very is fit to use for industrial community really, with after making lithium ion battery negative material in a large number and apace, its production line also can be enjoyed and pay much attention to security and administrative convenience.
Claims (13)
1. the preparation method of a lithium ion battery negative material, comprise: preparation one is mixed with a modification liquid of carbon back material, make it form carbon back material to make this carbon back material whereby once modification through a combination treatment, be placed on a non-oxidizing gas atmosphere afterwards and get off to carry out a drying treatment, and obtain this lithium ion battery negative material; It is characterized in that: this modification liquid includes a polar solvent and one first component or one second component, this first component has stannous fluoboric acid, fluoroboric acid, and thiocarbamide, this second component then has tin protochloride, Tripotassium Citrate, and following at least one alkaline agent: potassium hydroxide, lithium hydroxide, with sodium hydroxide.
2. the preparation method of lithium ion battery negative material according to claim 1 is characterized in that, in every liter modification liquid, the incorporation of this carbon back material is between 0.1 gram～600 grams; This combination treatment is to carry out to the ebullient temperature range at 60 ℃; This non-oxidizing gas atmosphere more includes the following hydrogen of 5vol%, and this drying treatment is not to be higher than 10
-2The holder atmospheric pressure value under, carry out in 20 ℃～150 ℃ temperature ranges.
3. the preparation method of lithium ion battery negative material according to claim 2 is characterized in that, in every liter modification liquid, the incorporation of this carbon back material is between 0.1 gram～450 grams; This combination treatment is to carry out in 60 ℃～90 ℃ temperature range.
4. the preparation method of lithium ion battery negative material according to claim 1, it is characterized in that, this carbon back material is selected certainly in intermediate phase Graphite Powder 99, Jie's phase carbon ball, ball-type carbon material, synthetic graphite, natural graphite, CNT (carbon nano-tube), hard carbon, or an above-mentioned combination; This polar solvent is selected certainly in water, alcohols, aldehydes, ketone, or an above-mentioned combination; This non-oxidizing gas atmosphere is nitrogen, rare gas element, carbonic acid gas, or an above-mentioned combination.
5. the preparation method of lithium ion battery negative material according to claim 1, it is characterized in that, this modification liquid includes this first component, and modification liquid in every liter, this modification liquid is dissolved with 0.01 mole～2 moles stannous fluoboric acid, 0.01 mole～2 moles fluoroboric acid, and 0.01 mole～5 moles thiocarbamide.
6. the preparation method of lithium ion battery negative material according to claim 5, it is characterized in that, in every liter modification liquid, this modification liquid is dissolved with 0.075 mole～1.25 moles stannous fluoboric acid, 0.1 mole～1 mole fluoroboric acid, and 0.5 mole～4 moles thiocarbamide.
7. the preparation method of lithium ion battery negative material according to claim 1, it is characterized in that, this modification liquid includes this second component, and modification liquid in every liter, this modification liquid is dissolved with 0.005 mole～3 moles tin protochloride, 0.005 mole～8 moles alkaline agent, and 0.005 mole～3 moles Tripotassium Citrate.
8. the preparation method of lithium ion battery negative material according to claim 7 is characterized in that, this modification liquid is dissolved with 0.05 mole～2 moles tin protochloride, 0.5 mole～2.5 moles alkaline agent, and 0.01 mole～1 mole Tripotassium Citrate.
9. a lithium ion battery negative material includes a carbon back material, and one attached to the material that adheres on this carbon base material surface, it is characterized in that this adheres to material and is discontinuously arranged particulate state, and the atomic quantity ratio of its sulphur and tin is between 0.8～1.2.
10. lithium ion battery negative material according to claim 9 is characterized in that, this atomic quantity ratio that adheres to sulphur and tin in the material is between 0.8667～1.0588.
11. lithium ion battery negative material according to claim 9 is characterized in that, this size range of adhering to material is between 3nm～200nm.
12. lithium ion battery negative material according to claim 11 is characterized in that, this size range of adhering to material is between 3nm～100nm.
13. lithium ion battery negative material according to claim 9 is characterized in that, is to make with preparation method according to claim 5.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103140968A (en) * | 2010-09-16 | 2013-06-05 | 电子部品研究院 | Anode active material, nonaqueous lithium secondary battery containing same, and preparation method thereof |
| CN104505503A (en) * | 2015-01-09 | 2015-04-08 | 高淑萍 | Method for preparing modified carbon-based negative electrode material |
| CN108963258A (en) * | 2018-07-11 | 2018-12-07 | 大同新成新材料股份有限公司 | A kind of porous carbon-based negative electrode material of surface low-level oxidation and preparation method thereof |
| CN112436127A (en) * | 2020-12-02 | 2021-03-02 | 天津工业大学 | Preparation method of novel nano-structure tin-carbon composite negative electrode material |
-
2008
- 2008-05-20 CN CNA2008101001044A patent/CN101585528A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103140968A (en) * | 2010-09-16 | 2013-06-05 | 电子部品研究院 | Anode active material, nonaqueous lithium secondary battery containing same, and preparation method thereof |
| CN103140968B (en) * | 2010-09-16 | 2016-01-20 | 电子部品研究院 | Active material of positive electrode, non-aqueous lithium secondary cell containing this active material of positive electrode and preparation method thereof |
| CN104505503A (en) * | 2015-01-09 | 2015-04-08 | 高淑萍 | Method for preparing modified carbon-based negative electrode material |
| CN108963258A (en) * | 2018-07-11 | 2018-12-07 | 大同新成新材料股份有限公司 | A kind of porous carbon-based negative electrode material of surface low-level oxidation and preparation method thereof |
| CN112436127A (en) * | 2020-12-02 | 2021-03-02 | 天津工业大学 | Preparation method of novel nano-structure tin-carbon composite negative electrode material |
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