CN104037412A - Preparation method of multilevel-structured hollow nano-sphere of negative electrode material of high-performance lithium ion secondary battery - Google Patents
Preparation method of multilevel-structured hollow nano-sphere of negative electrode material of high-performance lithium ion secondary battery Download PDFInfo
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Abstract
The invention relates to a preparation method of a multilevel-structured hollow nano-sphere of negative electrode material of a high-performance lithium ion secondary battery. The preparation method comprises the following steps: with a zinc source, a tin source and weak base as raw materials as well as surfactant polyacrylic acid (PAA) as a template, synthesizing a multilevel-structured hollow zinc hydroxystannate nano-sphere by virtue of a one-step hydrothermal method, wherein the diameter of the nano-sphere is 400-600nm; calcining in an air atmosphere, so as to obtain a morphology-maintained multilevel-structured zinc stannate nano-sphere structure. According to the preparation method, when the multilevel-structured hollow zinc hydroxystannate nano-sphere and a multilevel-structured zinc stannate nano-sphere are utilized as the negative electrode materials of the lithium ion secondary battery, both the two compounds show excellent electrochemical performance, high specific discharge capacity, good cycling stability and excellent rate capability; due to a specific multilevel structure, the hollow nano-sphere can provide a large surface area and a stable structure and can be widely applied to the fields of catalysis, the lithium ion secondary battery, solar cells and the like.
Description
Technical field
The preparation method who the present invention relates to the multilevel hierarchy nano-hollow ball that a kind of high performance lithium ion secondary battery negative material is comprised of nanometer rods, 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 commercialization of ion secondary battery cathode material lithium.Although material with carbon element has had very much progress at aspects such as electrochemistry cycle performance, security performances than lithium metal, but because of embedding lithium current potential and the lithium metal of material with carbon element close, thereby still there will be part lithium ion while overcharging to pile up and form Li dendrite in negative terminal surface, easily cause potential safety hazard.On the other hand, material with carbon element is when discharging and recharging for the first time, can be at phase (Solid Electrolyte Interface Film in the middle of active material Surface Creation solid electrolyte, be SEI film), produce the loss of larger irreversible capacity, also increased the impedance between electrode and electrolyte interface, thereby made Li
+embedding and deviate to become difficulty.Therefore the Novel anode material that new generation fail safe is good, specific capacity is high, have extended cycle life has become current top priority.
Tin-based composites, as: SnO
2, Zn
2snO
4, ZnSnO
3deng, inexpensive and environmentally friendly because of it, be the lithium ion battery negative material that a class has much potentiality.Zn
2snO
4there is higher theoretical specific capacity (1231mAh/g), far away higher than other lithium cell negative pole material of great majority, its voltage platform is higher than carbon electrode, thereby can suppress the security performance that improves battery of separating out of lithium metal, and there is the characteristics such as high conductivity, high electron mobility and low visible light absorption, inexpensive low toxicity, (J.Am.Chem.Soc. free from environmental pollution, 1991,113,855 – 861.).The Zn that has synthesized at present the special appearances such as octahedra shape, bar-shaped, cubic
2snO
4compound, but the deficiency that in most of document of having reported, also unresolved zinc special capacity fade in charge and discharge process is fast, 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 addition
2snO
4the reversible specific discharge capacity reaching is not at present very high, reason be have many-sided, not only relevant with preparation technology, also relevant with the Some features of himself, for example conductivity is not good, cyclical stability is poor, these shortcomings we can be by coated, the material etc. of preparing different-shape is improved accordingly.Material pattern is very large on physicochemical properties impact.Because there is the feature structures such as hollow, 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 some peculiar characteristic (Nature2002 based on microcosmic " parcel " effect, 420,395.; Adv.Mater.2003,15,832.).These unique character are widely used the aspects such as identification of hollow micro-nano structure transporting in life entity, DNA at lithium rechargeable battery material, catalysis, medicine.Concerning this material of zinc, the synthetic report of multistage spherical shape is relatively less, and its chemical property but has no report.In addition zinc hydroxyl stannate (ZnSn (OH),
6) be typical perovskite structure hydroxy compounds, be also a kind of transition metal stannate with changeable valence state, particular electrical minor structure, there is excellent photocatalysis, fire-retardant and but the performances such as cigarette.In zinc hydroxyl stannate crystal, metallic atom and oxygen atom ligand have formed Sn (OH)
6octahedral structure and Zn (OH)
6octahedral structure, the total oxygen atom in these octahedra edges and corners rises and is connected and bridge beam action, and then has formed the distinctive structural framing of zinc hydroxyl stannate.But the research used as ion secondary battery cathode material lithium has no report.
Summary of the invention
For the deficiencies in the prior art, the invention provides the preparation method of a kind of high performance lithium ion secondary battery negative material multilevel hierarchy nano zinc hydroxyl stannate hollow ball and multilevel hierarchy nano-zinc stannate hollow ball, preparation method of the present invention is easy and be easy to industrialization, and has 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, and Xi Yuan, weak base is raw material, the surfactant polyacrylic acid (PAA) of take is template, the multilevel hierarchy nano zinc hydroxyl stannate hollow ball of synthetic diameter 400～600nm; By the calcining under air atmosphere, obtained the multilevel hierarchy nano-zinc stannate hollow ball structure that pattern keeps again.When multilevel hierarchy nano zinc hydroxyl stannate hollow ball of the present invention and multilevel hierarchy nano-zinc stannate hollow ball are used as ion secondary battery cathode material lithium, two kinds of compounds all show excellent chemical property, and 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 3.3～20m mol/L zinc source and 0.138～0.56m mol/L 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;
(2) by 2.5～20m mol/L Xi Yuan, in Xi Yuan and distilled water mass ratio, be: ratio 1:(50-150) adds in distilled water, make the tin source aqueous solution, 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 ℃ of conditions after, after centrifugal treating, under 60～80 ℃ of conditions, under vacuum condition, dry, make multilevel hierarchy nano zinc hydroxyl stannate hollow ball.
Preferred according to the present invention, a kind of preparation method of high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball, 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 ℃/min, calcining heat is 500～650 ℃, calcination time is 2～6h, makes multilevel hierarchy nano-zinc stannate hollow ball.
The multilevel hierarchy nano zinc hydroxyl stannate hollow ball of invention and multilevel hierarchy nano-zinc stannate hollow ball all can be used as ion secondary battery cathode material lithium and use.
The present invention is preferred, and 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.
The present invention is preferred, and described Xi Yuan is selected from one of tin ash, stannous oxide, four water sodium stannates, sodium stannate trihydrate, stannous chloride, 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 one of NaOH, potassium hydroxide, sodium carbonate, sodium acid carbonate, hydrazine hydrate, ammoniacal liquor or combination.
The present invention is preferred, and in step (3), the reaction temperature of reactor is 180 ℃, 24 hours reaction time.
The present invention is preferred, and in step (4), optimum calcinating temperature is 600 ℃, 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 1～4m mol and 0.25g～1.0g, join in 20～30mL distilled water, stir 20～30min, make mixed solution;
(2) Xi Yuan of 1.5～2.0m mol is joined in 5～15mL distilled water, make the tin source aqueous solution, the tin source aqueous solution is dropped in the mixed solution of step (1), stir 20～30min, make ZnSn (OH)
6dirty solution;
(3) at ZnSn (OH)
6in dirty solution, drip aqueous slkali 2～10mL, stir after 20～30min, be transferred in the reactor of 60～100ml, reactor is put into baking oven, heat 20～24 hours under 160～180 ℃ of conditions after, naturally cool to room temperature, after centrifugal treating, under 60～80 ℃ of conditions, under vacuum condition, dry, make the ZnSn (OH) of multi-stage hollow spherical structure
6compound;
(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 crucible furnace, under air atmosphere, calcine, the heating rate of crucible furnace is 2～10 ℃/min, calcining heat is 500～650 ℃, calcination time 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 6-24m mol.
Further preferred, described aqueous slkali is selected from hydrazine hydrate or ammoniacal liquor, the mass fraction 50wt% of described hydrazine hydrate, and the mass fraction of ammoniacal liquor is 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 the purity of reaction raw materials does not have a significant effect to the formation of end product and performance, if reaction raw materials can be technical pure, and chemical pure or analyze purely, production cost is low;
(b) the multilevel hierarchy nano zinc hydroxyl stannate hollow ball that prepared by the present invention and multilevel hierarchy nano-zinc stannate hollow ball all can be used as ion secondary battery cathode material lithium and use, after 888 circle circulations, still can reach 663.8mAh/g, all there is good high rate performance, 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 other a large amount of molecules or large-sized object, the peculiar characteristic based on microcosmic " parcel " effect, makes it have good high rate performance.
(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 can obtain final products after a hydro-thermal, and product does not need reprocessing; Cost is low, is suitable for industrial large-scale production;
(d) course of reaction Environmental Safety, produces without poisonous and harmful substance.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the multilevel hierarchy nano zinc hydroxyl stannate hollow ball of embodiment 1 preparation, and wherein left ordinate is intensity, and abscissa is angle of diffraction (2 θ);
Fig. 2 is the XRD figure of the multilevel hierarchy nano-zinc stannate hollow ball of embodiment 2 preparations, and wherein left ordinate is intensity, and abscissa 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 of embodiment 1 preparation,
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 of embodiment 2 preparations,
Wherein, a, the scanning electron microscope (SEM) photograph that b figure is zinc; C is the transmission electron microscope picture of zinc.
Fig. 5 is the multilevel hierarchy nano zinc hydroxyl stannate hollow ball electrochemical property test result of embodiment 1 preparation.
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 the multilevel hierarchy nano-zinc stannate hollow ball electrochemical property test result of embodiment 2 preparations.
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).
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be appreciated that, these examples are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that, after having read content set forth in the present invention, those skilled in the art can make various changes or modifications the present invention, 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 2m mol (CHCOO)
22H
2o, 0.75g PAA are dissolved in the distilled water of 25mL, stir 30min; By the Na of 1.9m mol
2snO34H
2the distilled water that O is dissolved in 10mL is mixed with solution, is added dropwise in above-mentioned mixed liquor, continues to stir 30min; In above-mentioned white casse liquid, drip 6mL NH
3h
2o, stirs after 30min, above-mentioned mixed liquor is transferred in the reactor of 60mL, at 180 ℃ of temperature, maintains 24h.Question response still is cooled to after room temperature, by gained white product through centrifugal several times of absolute ethyl alcohol, distilled water, 60 ℃ of oven dry under vacuum condition after collection of products, gained white product i.e. the multilevel hierarchy nano zinc hydroxyl stannate hollow ball for being comprised of nanometer rods.The XRD figure of multilevel hierarchy nano zinc hydroxyl stannate hollow ball, SEM photo and TEM figure are as shown in figures 1 and 3.
Embodiment 2
Multilevel hierarchy nanometer Zn
2snO
4the 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 6h at 600 ℃, heating rate is 5 ℃/min.Products therefrom is the zinc hollow ball of hollow Nano.The XRD figure of multilevel hierarchy nano-zinc stannate hollow ball, SEM photo and TEM figure are as shown in Figure 2 and Figure 4.
Embodiment 3
Properties of product test
Two kinds of products of zinc hollow ball that the zinc hydroxyl stannate hollow ball that embodiment 1 makes and embodiment 2 make are as 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, take distilled water as solvent, make cathode size, be coated on the Copper Foil of 12mm, after fully dry compressing tablet, obtain negative plate.Battery anode slice lithium sheet.In the glove box of inert gas shielding, the LiPF6/EC/DMC/DEC (1:1:1) of 1mol/L of take is electrolyte, and Celgerd2300 is barrier film, is assembled into 2320 type button cells.Tester: discharge and recharge instrument (Land); JEM-1011 transmission electron microscope, Bruker D8-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 is 1000mA/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 battery as shown in figure (6a) shows: initial discharge capacity reaches 1190.1mAh/g, after 60 circle circulations, still can reach 442.8mAh/g.
As shown in Fig. 5 b and 6b, gained zinc hydroxyl stannate and zinc battery all have good high rate performance.
Claims (10)
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 3.3～20m mol/L zinc source and 0.138～0.56m mol/L 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;
(2) by 2.5～20m mol/L Xi Yuan, in Xi Yuan and distilled water mass ratio, be: 1:(50-150)) ratio add in distilled water, make the tin source aqueous solution, 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 ℃ of conditions after, after centrifugal treating, under 60～80 ℃ of conditions, under vacuum condition, dry, make multilevel hierarchy nano zinc hydroxyl stannate hollow ball.
2. 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, 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 ℃/min, calcining heat is 500～650 ℃, 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, it is characterized in that, described Xi Yuan is selected from one of tin ash, stannous oxide, four water sodium stannates, sodium stannate trihydrate, stannous chloride, 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 ℃, 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 1, is characterized in that, in step (4), optimum calcinating temperature is 600 ℃, and calcination time is 6h.
8. the preparation method of high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball claimed in claim 1, comprises that step is as follows:
(1) by the polyacrylic acid (PAA) of the zinc source of 1～4m mol and 0.25g～1.0g, join in 20～30mL distilled water, stir 20～30min, make mixed solution;
(2) Xi Yuan of 1.5～2.0m mol is added in 5～15mL distilled water, make the tin source aqueous solution, the tin source aqueous solution is dropped in the mixed solution of step (1), stir 20～30min, make ZnSn (OH)
6dirty solution;
(3) at ZnSn (OH)
6in dirty solution, drip aqueous slkali 2～10mL, stir after 20～30min, be transferred in the reactor of 60～100ml, reactor is put into baking oven, heat 20～24 hours under 160～180 ℃ of conditions after, naturally cool to room temperature, after centrifugal treating, under 60～80 ℃ of conditions, under vacuum condition, dry, make the ZnSn (OH) of multi-stage hollow spherical structure
6compound;
(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 crucible furnace, under air atmosphere, calcine, the heating rate of crucible furnace is 2～10 ℃/min, calcining heat is 500～650 ℃, calcination time is 2～6h, makes multilevel hierarchy nano-zinc stannate hollow ball.
9. the preparation method of high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball according to claim 8, is characterized in that, described aqueous slkali is selected from NaOH, potassium hydroxide, sodium carbonate or sodium acid carbonate, and consumption is 6-24m mol; Described aqueous slkali is selected from hydrazine hydrate or ammoniacal liquor, the mass fraction 50wt% of described hydrazine hydrate, and the mass fraction of ammoniacal liquor is 25-28wt%, consumption is 6～8ml.
10. the preparation method of high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball according to claim 8, is characterized in that, in step (1), polyacrylic consumption is 0.75g.
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| CN104609462A (en) * | 2015-01-09 | 2015-05-13 | 陕西科技大学 | Preparation method of hollow spherical nano tin electrode material for sodium ion battery cathodes |
| CN105405656A (en) * | 2015-11-30 | 2016-03-16 | 福州大学 | Hierarchical structure Zn<2>SnO<4> and application thereof |
| CN105449177A (en) * | 2015-11-30 | 2016-03-30 | 中南大学 | Porous cubic ZnSO3@graphene negative electrode material used for sodium ion battery and preparation method for porous cubic ZnSO3@graphene negative electrode material |
| 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 |
| CN110247033A (en) * | 2019-05-29 | 2019-09-17 | 广东工业大学 | A kind of SnS@NSC core-bivalve cube structure composite material and preparation method and application |
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| CN116947086A (en) * | 2023-08-01 | 2023-10-27 | 东北师范大学 | Pomegranate type Zn 2 SnO 4 Preparation method and application of nano flame retardant |
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| CN104609462A (en) * | 2015-01-09 | 2015-05-13 | 陕西科技大学 | Preparation method of hollow spherical nano tin electrode material for sodium ion battery cathodes |
| CN105405656A (en) * | 2015-11-30 | 2016-03-16 | 福州大学 | Hierarchical structure Zn<2>SnO<4> and application thereof |
| CN105449177A (en) * | 2015-11-30 | 2016-03-30 | 中南大学 | Porous cubic ZnSO3@graphene negative electrode material used for sodium ion battery and preparation method for porous cubic ZnSO3@graphene negative electrode material |
| 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 |
| CN110247033A (en) * | 2019-05-29 | 2019-09-17 | 广东工业大学 | A kind of SnS@NSC core-bivalve cube structure composite material and preparation method and 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 |
| CN111613788A (en) * | 2020-06-05 | 2020-09-01 | 哈尔滨工业大学（威海） | Hollow spherical lithium nickel manganese oxide positive electrode material and preparation method 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 |
| CN116947086A (en) * | 2023-08-01 | 2023-10-27 | 东北师范大学 | Pomegranate type Zn 2 SnO 4 Preparation method and application of nano flame retardant |
| 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 |
| CN118352620B (en) * | 2024-04-08 | 2024-11-05 | 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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