CN104037412B - The preparation method of high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball - Google Patents
The preparation method of high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of high performance lithium ion secondary battery negative material multilevel hierarchy nano zinc hydroxyl stannate hollow ball, adopt one step hydro thermal method, with zinc source, Xi Yuan, weak base is raw material, taking surfactant polyacrylic acid (PAA) as template, the multilevel hierarchy nano zinc hydroxyl stannate hollow ball of synthetic diameter 400～600nm; By calcining, obtain the multilevel hierarchy nano-zinc stannate hollow ball structure that pattern keeps again under air atmosphere. When multilevel hierarchy nano zinc hydroxyl stannate hollow ball of the present invention and multilevel hierarchy nano-zinc stannate hollow ball all can be used as ion secondary battery cathode material lithium, two kinds of compounds all show excellent chemical property, specific discharge capacity is higher, cyclical stability is better, high rate performance is excellent, the multilevel hierarchy of uniqueness of the present invention can provide larger surface area and stable structure more, can be widely used in the fields such as catalysis, lithium rechargeable battery, solar cell.
Description
Technical field
The present invention relates to multilevel hierarchy nano-hollow ball that a kind of high performance lithium ion secondary battery negative material is made up of nanometer rodsPreparation method, belongs to technical field of lithium ion.
Background technology
Negative material is one of critical material affecting performance of lithium-ion secondary battery quality. At present, the material with carbon element such as graphite is as lithiumThe commercialization of ion secondary battery negative material. Although material with carbon element compares metal at aspects such as electrochemistry cycle performance, security performancesLithium has had very much progress, but because embedding lithium current potential and the lithium metal of material with carbon element are close, still there will be part lithium ion while overcharging to existThereby negative terminal surface is piled up and is formed Li dendrite, easily causes potential safety hazard. On the other hand, material with carbon element in the time discharging and recharging for the first time, meetingPhase (SolidElectrolyteInterfaceFilm, i.e. SEI film) in the middle of active material Surface Creation solid electrolyte, producesThe loss of larger irreversible capacity, has also increased the impedance between electrode and electrolyte interface, thereby makes Li+Embedding and deviate fromBecome difficulty. Therefore the Novel anode material that new generation security is good, specific capacity is high, have extended cycle life has become currentTop priority.
Tin-based composites, as: SnO2、Zn2SnO4、ZnSnO3Deng, inexpensive and environmentally friendly because of it, be that a class has much latentThe lithium ion battery negative material of power. Zn2SnO4There is higher theoretical specific capacity (1231mAh/g), far away higher than great majorityOther lithium cell negative pole material, its voltage platform is higher than carbon electrode, thereby can suppress the security that improves battery of separating out of lithium metalCan, and there is the characteristics such as high conductivity, high electron mobility and low visible light absorption, inexpensive low toxicity, (J.Am. free from environmental pollutionChem.Soc., 1991,113,855 – 861.). The special appearances such as octahedra shape, bar-shaped, cubic are synthesized at presentZn2SnO4Compound, but in most of document of having reported and unresolved zinc stannate special capacity fade in charge and discharge process is fast,The deficiency that high rate performance is poor, and conventionally in document, only studied 50 charge-discharge performances that enclose, the circulation number of turns is less. Zn in addition2SnO4The reversible specific discharge capacity reaching is not at present very high, reason be have many-sided, not only relevant with preparation technology, also and itsThe Some features of self is relevant, and for example electric conductivity is not good, and cyclical stability is poor, and it is coated that we can pass through these shortcomings,Material of preparing different-shape etc. is improved accordingly. Material pattern is very large on physicochemical properties impact. Because have hollow,The feature structure such as low-density and high-specific surface area, multi-stage hollow micro-nano structure shows the character of many uniquenesses, as heat insulation, sound insulation,Electric insulation, can hold other a large amount of molecules or large-sized object, can produce like this that some are peculiar in microcosmic " parcel "Characteristic (Nature2002,420,395. of effect; Adv.Mater.2003,15,832.). These unique character make hollow micro-nanoThe aspects such as the identification of structure transporting in life entity, DNA at lithium rechargeable battery material, catalysis, medicine obtain widelyApplication. Concerning this material of zinc stannate, the synthetic report of multistage spherical shape is relatively less, and its chemical property does not but appear in the newspapersRoad. In addition zinc hydroxyl stannate (ZnSn (OH),6) be typical perovskite structure hydroxy compounds, be also one have changeable valence state,The transition metal stannate of particular electrical minor structure, has excellent photocatalysis, fire-retardant and but the performances such as cigarette. At zinc hydroxyl stannate crystalline substanceIn body, metallic atom and oxygen atom ligand have formed Sn (OH)6Octahedral structure and Zn (OH)6Octahedral structure, these octahedralsThe total oxygen atom in body edges and corners rises and is connected and bridge beam action, and then has formed the distinctive structural framing of zinc hydroxyl stannate. But willIts research as ion secondary battery cathode material lithium but has no report.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of high performance lithium ion secondary battery negative material multilevel hierarchy nanometer hydroxylThe preparation method of base zinc stannate hollow ball and multilevel hierarchy nano-zinc stannate hollow ball, preparation method of the present invention is easy and be easy toIndustrialization, and effectively controlled the synthetic of two kinds of multilevel hierarchy compounds.
Summary of the invention:
The present invention adopts one step hydro thermal method, with zinc source, Xi Yuan, weak base is raw material, taking surfactant polyacrylic acid (PAA) asTemplate, the multilevel hierarchy nano zinc hydroxyl stannate hollow ball of synthetic diameter 400～600nm; Again by forging under air atmosphereBurn, obtained the multilevel hierarchy nano-zinc stannate hollow ball structure that pattern keeps. Multilevel hierarchy nano zinc hydroxyl stannate of the present inventionWhen hollow ball and multilevel hierarchy nano-zinc stannate hollow ball are used as ion secondary battery cathode material lithium, two kinds of compounds all showExcellent chemical property, specific discharge capacity is higher, cyclical stability is better, high rate performance is excellent.
Technical scheme of the present invention is as follows:
A preparation method for high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball, comprises that step is as follows:
(1) by 3.3～20mmol/L zinc source and 0.138～0.56mmol/L polyacrylic acid, join in distilled water instituteStating zinc source, polyacrylic acid, distilled water mass ratio is: 1:(0.1-0.6): (120-500), stir 20～30min, make mixingSolution; Described polyacrylic weight average molecular weight is 3000～5000;
(2) by 2.5～20mmol/L Xi Yuan in Xi Yuan and distilled water mass ratio be: ratio 1:(50-150) adds distillationIn water, make the tin source aqueous solution, the tin source aqueous solution dropped in the mixed solution of step (1), continue to stir 20～30min,Obtain white casse liquid, the mass ratio in the addition of Xi Yuan and zinc source is: 1:1;
(3), in the white casse liquid obtaining to step (2), drip the aqueous slkali of 0.6mol/L, the addition of aqueous slkali and zincThe mass ratio in source is (20～30): 1, after magnetic agitation 20～30min, be transferred in the reactor of 60～100ml, and will reactStill is put into baking oven, naturally cools to room temperature after heating 6～24 hours under 160～200 DEG C of conditions, after centrifugal treating 60～80 DEG CUnder condition, under vacuum condition, dry, make multilevel hierarchy nano zinc hydroxyl stannate hollow ball.
Preferred according to the present invention, a kind of preparation side of high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ballMethod, also comprises the steps:
Get the multilevel hierarchy nano zinc hydroxyl stannate hollow ball that step (3) makes and be placed in porcelain boat, porcelain boat is put into crucible furnace,Under air atmosphere, calcine, the heating rate of crucible furnace is 2～10 DEG C/min, and calcining heat is 500～650 DEG C, and calcination time is2～6h, makes multilevel hierarchy nano-zinc stannate hollow ball.
Multilevel hierarchy nano zinc hydroxyl stannate hollow ball and the multilevel hierarchy nano-zinc stannate hollow ball of invention all can be used as lithium ion twoPrimary cell negative material uses.
The present invention is preferred, and described zinc source is selected from zinc oxalate, zinc acetate, zinc nitrate, zinc chloride, basic zinc carbonate, di(2-ethylhexyl)phosphateOne of hydrogen zinc, zinc oxide, zinc sulfate or combination.
The present invention is preferred, and described Xi Yuan is selected from tin ash, stannous oxide, four water sodium stannates, sodium stannate trihydrate, protochlorideOne of tin, butter of tin, the sub-tin of nitric acid, stannous sulfate or combination.
The present invention is preferred, and the aqueous slkali in described step (3) is selected from NaOH, potassium hydroxide, sodium carbonate, bicarbonateOne of sodium, hydrazine hydrate, ammoniacal liquor or combination.
The present invention is preferred, and in step (3), the reaction temperature of reactor is 180 DEG C, 24 hours reaction time.
The present invention is preferred, and in step (4), optimum calcinating temperature is 600 DEG C, and calcination time is 6h.
Preferred embodiments of the present invention are as follows:
A preparation method for high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball, comprises that step is as follows:
(1), by the polyacrylic acid (PAA) of the zinc source of 1～4mmol and 0.25g～1.0g, join 20～30mL distillationIn water, stir 20～30min, make mixed solution;
(2) Xi Yuan of 1.5～2.0mmol is joined in 5～15mL distilled water, make the tin source aqueous solution, by Xi YuanshuiSolution drops in the mixed solution of step (1), stirs 20～30min, makes ZnSn (OH)6Dirty solution;
(3) at ZnSn (OH)6In dirty solution, drip aqueous slkali 2～10mL, stir after 20～30min, be transferred to 60～100mlReactor in, reactor is put into baking oven, naturally cool to room temperature heat 20～24 hours under 160～180 DEG C of conditions after,After centrifugal treating, under 60～80 DEG C of conditions, under vacuum condition, dry, make the ZnSn (OH) of multi-stage hollow spherical structure6Compound;
(4) get the multilevel hierarchy nano zinc hydroxyl stannate hollow ball that step (3) makes and be placed in porcelain boat, porcelain boat is put into crucibleIn stove, under air atmosphere, calcine, the heating rate of crucible furnace is 2～10 DEG C/min, and calcining heat is 500～650 DEG C, calciningTime is 2～6h, makes multilevel hierarchy nano-zinc stannate hollow ball.
Further preferred, described aqueous slkali is selected from NaOH, potassium hydroxide, sodium carbonate or sodium acid carbonate, and consumption is 6-24mmol。
Further preferred, described aqueous slkali is selected from hydrazine hydrate or ammoniacal liquor, the mass fraction 50wt% of described hydrazine hydrate, ammoniacal liquorMass fraction be 25-28wt%, consumption is 6～8ml.
The present invention is preferred, and in step (1), polyacrylic consumption is 0.75g.
Beneficial effect of the present invention is as follows:
(a) preparation method of the present invention is easy to implement, and formation and the performance of the purity of reaction raw materials to end product do not have obvious shadowRing, if reaction raw materials can be technical pure, chemical pure or analyze purely, production cost is low;
(b) multilevel hierarchy nano zinc hydroxyl stannate hollow ball and the multilevel hierarchy nano-zinc stannate hollow ball that prepared by the present invention all can be doneFor ion secondary battery cathode material lithium uses, after 888 circle circulations, still can reach 663.8mAh/g, all there is good multiplying powerPerformance, two kinds of products all have the feature of hollow, low-density and high-specific surface area, heat insulation, sound insulation, electric insulation, can hold largeOther molecule or large-sized object of amount, the peculiar characteristic based on microcosmic " parcel " effect, makes it have good doubly forthrightEnergy.
(c) the simple power consumption of the inventive method technique is few, only needs in crucible furnace, to divide at a lower temperature temperature section calcining after a hydro-thermalCan obtain final products, product does not need post processing; Cost is low, is suitable for industrial large-scale production;
(d) course of reaction Environmental Safety, produces without poisonous and harmful substance.
Brief description of the drawings
Fig. 1 is the XRD figure of the multilevel hierarchy nano zinc hydroxyl stannate hollow ball prepared of embodiment 1, and wherein left ordinate is intensity,Abscissa is angle of diffraction (2 θ);
Fig. 2 is the XRD figure of the multilevel hierarchy nano-zinc stannate hollow ball prepared of embodiment 2, and wherein left ordinate is intensity, horizontal strokeCoordinate is angle of diffraction (2 θ);
Fig. 3 is SEM photo and the TEM figure of the multilevel hierarchy nano zinc hydroxyl stannate hollow ball prepared of embodiment 1,
Wherein, a, the scanning electron microscope (SEM) photograph that b figure is zinc hydroxyl stannate; C is the transmission electron microscope picture of zinc hydroxyl stannate.
Fig. 4 is SEM photo and the TEM figure of the multilevel hierarchy nano-zinc stannate hollow ball prepared of embodiment 2,
Wherein, a, the scanning electron microscope (SEM) photograph that b figure is zinc stannate; C is the transmission electron microscope picture of zinc stannate.
Fig. 5 is multilevel hierarchy nano zinc hydroxyl stannate hollow ball electrochemical property test result prepared by embodiment 1.
Wherein, a is cycle performance figure, and b is high rate performance figure, and the left ordinate of two figure is all specific capacities, specific capacity unit:Every gram of MAH (mAh/g), abscissa is all the circulation number of turns (n).
Fig. 6 is multilevel hierarchy nano-zinc stannate hollow ball electrochemical property test result prepared by embodiment 2.
Wherein, a is cycle performance figure, and b is high rate performance figure, and the left ordinate of two figure is all specific capacities, specific capacity unit:Every gram of MAH (mAh/g), abscissa is all the circulation number of turns (n).
Detailed description of the invention
Below in conjunction with specific embodiment, further set forth the present invention. Should be appreciated that, these examples only need not for the present invention is describedIn limiting the scope of the invention. In addition should be understood that those skilled in the art can after having read content set forth in the present inventionSo that the present invention is made various changes or modifications, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
Multilevel hierarchy nanometer ZnS n (OH)6The preparation of hollow ball
By the Zn of 2mmol (CHCOO)2·2H2O, 0.75gPAA are dissolved in the distilled water of 25mL, stir 30min; WillThe Na of 1.9mmol2SnO3·4H2The distilled water that O is dissolved in 10mL is mixed with solution, is added dropwise in above-mentioned mixed liquor, continuesStir 30min; In above-mentioned white casse liquid, drip 6mLNH3·H2O, stirs after 30min, and above-mentioned mixed liquor is shiftedTo the reactor of 60mL, at 180 DEG C of temperature, maintain 24h. Question response still is cooled to after room temperature, by gained white productThrough centrifugal several times of absolute ethyl alcohol, distilled water, 60 DEG C of oven dry under vacuum condition after collection of products, gained white product serves as reasonsThe multilevel hierarchy nano zinc hydroxyl stannate hollow ball of nanometer rods composition. The XRD figure of multilevel hierarchy nano zinc hydroxyl stannate hollow ball,SEM photo and TEM scheme as shown in figures 1 and 3.
Embodiment 2
Multilevel hierarchy nanometer Zn2SnO4The preparation of hollow ball
The hydroxyl stannate zinc compound obtaining is got in right amount, be evenly laid in porcelain boat, be positioned in crucible furnace, calcine 6 at 600 DEG CH, heating rate is 5 DEG C/min. Products therefrom is the zinc stannate hollow ball of hollow Nano. Multilevel hierarchy nano-zinc stannate is hollowXRD figure, SEM photo and the TEM of ball scheme as shown in Figure 2 and Figure 4.
Embodiment 3
Properties of product test
Two kinds of products of zinc stannate hollow ball that the zinc hydroxyl stannate hollow ball that embodiment 1 makes and embodiment 2 make are as lithium ion twoPrimary cell negative material, adopts rubbing method to prepare electrode, by raw material active material in mass ratio: acetylene black: CMC=60:30:10Ratio mix, taking distilled water as solvent, make cathode size, be coated on the Copper Foil of 12mm, must after fully dry compressing tabletTo negative plate. Battery anode slice lithium sheet. In the glove box of inert gas shielding, with 1mol/L'sLiPF6/EC/DMC/DEC (1:1:1) is electrolyte, and Celgerd2300 is barrier film, is assembled into 2320 type button cells. SurveyTest instrument: discharge and recharge instrument (Land); JEM-1011 transmission electron microscope, BrukerD8-X x ray diffractometer x.
Test result
On blue electric tester, carry out battery charging/discharging performance testing, discharge and recharge condition: voltage range 0.01～3.0v, current density is1000mA/g；
The cycle performance curve of the hydroxyl stannate zinc battery as shown in figure (5a) shows: initial discharge capacity reaches 729.1mAh/g,After 888 circle circulations, still can reach 663.8mAh/g;
The cycle performance curve of the zinc stannate battery as shown in figure (6a) shows: initial discharge capacity reaches 1190.1mAh/g, warpAfter 60 circle circulations, still can reach 442.8mAh/g.
As shown in Fig. 5 b and 6b, gained zinc hydroxyl stannate and zinc stannate battery all have good high rate performance.
Claims (7)
1. a preparation method for high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball, comprises that step is as follows:
(1) by zinc source and polyacrylic acid, join in distilled water, described zinc source, polyacrylic acid, distilled water mass ratio are: 1:(0.1-0.6): (120-500), stir 20 ~ 30min, make mixed solution; Described polyacrylic weight average molecular weight is 3000～5000; In mixed solution, zinc source molar concentration is 3.3～20mmol/L, and polyacrylic acid molar concentration is 0.138～0.56mmol/L;
(2) Xi Yuan in Xi Yuan and distilled water mass ratio is: 1:(50-150)) ratio add in distilled water, make the tin source aqueous solution, the molar concentration of the tin source aqueous solution is 2.5～20mmol/L; The tin source aqueous solution is dropped in the mixed solution of step (1), continue to stir 20 ~ 30min, obtain white casse liquid, the mass ratio in the addition of Xi Yuan and zinc source is: 1:1;
(3) in the white casse liquid obtaining to step (2), drip the aqueous slkali of 0.6mol/L, the mass ratio in the addition of aqueous slkali and zinc source is (20～30): 1, after magnetic agitation 20 ~ 30min, be transferred in the reactor of 60 ~ 100ml, reactor is put into baking oven, naturally cool to room temperature heat 6 ~ 24 hours under 160 ~ 200 DEG C of conditions after, after centrifugal treating, under 60 ~ 80 DEG C of conditions, under vacuum condition, dry, make multilevel hierarchy nano zinc hydroxyl stannate hollow ball; The hollow ball making is made ion secondary battery cathode material lithium, adopt rubbing method to prepare electrode, by raw material active material in mass ratio: the ratio of acetylene black: CMC=60:30:10 is mixed, taking distilled water as solvent, make cathode size, be coated on the Copper Foil of 12mm, after fully dry compressing tablet, obtain negative plate.
2. the preparation method of high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball according to claim 1, it is characterized in that, also comprise the steps: to get the multilevel hierarchy nano zinc hydroxyl stannate hollow ball that step (3) makes and be placed in porcelain boat, porcelain boat is put into crucible furnace, under air atmosphere, calcine, the heating rate of crucible furnace is 2 ~ 10 DEG C/min, and calcining heat is 500 ~ 650 DEG C, calcination time is 2 ~ 6h, makes multilevel hierarchy nano-zinc stannate hollow ball.
3. the preparation method of high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball according to claim 1, it is characterized in that, described zinc source is selected from one of zinc oxalate, zinc acetate, zinc nitrate, zinc chloride, basic zinc carbonate, zinc dihydrogen phosphate, zinc oxide, zinc sulfate or combination.
4. the preparation method of high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball according to claim 1, is characterized in that, described Xi Yuan is selected from tin ash, stannous oxide, four water sodium stannates, sodium stannate trihydrate, protochloride
One of tin, butter of tin, the sub-tin of nitric acid, stannous sulfate or combination.
5. the preparation method of high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball according to claim 1, it is characterized in that, the aqueous slkali in described step (3) is selected from one of NaOH, potassium hydroxide, sodium carbonate, sodium acid carbonate, hydrazine hydrate, ammoniacal liquor or combination.
6. the preparation method of high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball according to claim 1, is characterized in that, in step (3), the reaction temperature of reactor is 180 DEG C, 24 hours reaction time.
7. the preparation method of high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball according to claim 2, is characterized in that, in step (4), calcining heat is 600 DEG C, and calcination time is 6h.
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| CN105489890A (en) * | 2015-11-30 | 2016-04-13 | 许昌学院 | Copper hydroxystannate micro-nano particles for lithium ion battery negative electrode and preparation method |
| CN105449177B (en) * | 2015-11-30 | 2018-02-06 | 中南大学 | A kind of porous cube of ZnSnO for sodium-ion battery3@graphene negative materials and preparation method thereof |
| CN105405656B (en) * | 2015-11-30 | 2018-07-20 | 福州大学 | A kind of graded structure Zn2SnO4And its application |
| CN110247033B (en) * | 2019-05-29 | 2020-12-08 | 广东工业大学 | SnS @ NSC core-double-shell cubic structure composite material and preparation method and application thereof |
| CN111613788B (en) * | 2020-06-05 | 2022-10-14 | 哈尔滨工业大学（威海） | Hollow spherical lithium nickel manganese oxide positive electrode material and preparation method thereof |
| CN116947086B (en) * | 2023-08-01 | 2024-03-05 | 东北师范大学 | Pomegranate type Zn 2 SnO 4 Preparation method and application of nano flame retardant |
| CN118352620A (en) * | 2024-04-08 | 2024-07-16 | 重庆太蓝新能源有限公司 | Polymer solid electrolyte, polymer solid electrolyte membrane, preparation method and application thereof |
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