CN106299309A - Graphene half cladding tin oxide nano particles cluster composite material and preparation method thereof - Google Patents
Graphene half cladding tin oxide nano particles cluster composite material and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of Graphene half cladding tin oxide nano particles cluster composite material and preparation method thereof, comprise the following steps: under (1) stirring, surfactant is dissolved in the tin ash hydrosol；(2) glucide and small flake diameter graphene oxide are added, and continuously stirred, obtain uniform presoma disperse system；(3) presoma disperse system is carried out hydrothermal treatment consists, produce black precipitate；(4) black precipitate is dried with calcination processing after, obtain Graphene half cladding tin oxide nano particles cluster composite.Compared with prior art, the product that the present invention prepares is when as electrode material, can effectively slow down the generation of solid electrolyte interface layer, what is more important can make lithium/sodium ion embed more at high speed and deviate from, and is greatly improved the material reversible charge/discharge capacity under big electric current.
Description
Technical field
The present invention relates to tin ash/graphene composite negative pole preparation field, relate to a kind of Graphene half cladding two
Tin oxide nanoparticles cluster composite material and preparation method thereof, the composite prepared can be used as ion battery/sodium ion electricity
Pond negative material.
Background technology
The electrochemistry capacitance relatively low due to the conventional graphite negative material used in lithium ion battery and poor discharge and recharge
Cyclical stability, people be devoted to explore there is high power capacity, the Novel cathode material for lithium ion battery of high stability has exceeded 20
Year.The metal-oxides such as stannum oxide, ferrum oxide, cobalt oxide, manganese oxide have the high theoretical capacity of about 1000mAh/g, always
The focus of this area research.Wherein, tin ash owing to it is cheap, be easy to get, and low toxicity, the characteristic of environmental protection, be most potential
One of a new generation's lithium ion battery negative material.But due to poor electric conductivity, and due to the play occurred in charge and discharge process
Broken, reunion and solid-electrolyte interface phase layer (SEI layer) that strong change in volume causes generate the loss to active substance, make
Tin dioxide material is difficult to have breakthrough in stability with on the life-span as lithium ion battery negative.
The crystal grain of tin ash is controlled at Nano grade, and the material with carbon elements such as tin ash and Graphene is carried out multiple
Close, be the approach of two kinds of maximally effective its performances of raising.Control crystal grain, at Nano grade, is especially small enough to quantum dot rank (＜
10nm), the stannic oxide particle die break that violent volumetric expansion is brought in charge and discharge process and reunion can effectively be slowed down
Problem, and shorten lithium ion in the transmission path within tin ash.
The existing method preparing tin ash/graphene combination electrode material is preparation-obtained mostly is tin ash
Grain is dispersed in the planar structure composite on two-dimensional graphene surface, and in product, stannic oxide particle size is relatively big, causes material
Material is when as lithium ion battery negative material, and lithium ion is more difficult to be transmitted the most wherein, have impact on material greatly
Performance under electric current；Simultaneously because tin ash is dispersed in graphenic surface, direct and electrolyte contacts, it is impossible to effectively limit
The formation of SEI layer, causes the cycle life of material to be greatly shortened.
Chinese patent CN104218232A discloses the tin dioxide lithium ion battery negative pole material of a kind of graphene modified
Preparation method, the method is in the solution by molten with electronegative graphene oxide for the hydrogen tin ash colloidal sol with positive charge
Glue mixes, and utilizes electrostatic force to carry out copolymerization and sinks and obtain the precipitation of both mixture, and calcines after cleaning-drying and obtain
Whole electrode material.In material prepared by the method, stannic oxide particle is only distributed in graphenic surface, causes it at big electric current
Under performance unsatisfactory, after 50 circulations of different size of multiplying power current charge-discharge electricity, capacity declines substantially.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and a kind of Graphene half cladding is provided
Tin oxide nano particles cluster composite material and preparation method thereof.Tin oxide nano particles is configured with many by this preparation method
The cluster of pore structure, and with graphene coated outside cluster, effectively limit the formation of SEI layer, simultaneously half cladding of Graphene
Structure is that path has been reserved in the transmission of lithium/sodium ion so that it is still has higher performance under big electric current during discharge and recharge, obtains
Composite for the negative material of lithium ion battery/sodium-ion battery, there is under big electric current more high power capacity, have simultaneously
Preferably charge and discharge circulation life.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of Graphene half cladding tin oxide nano particles cluster composite material and preparation method thereof, comprises the following steps:
(1), under stirring, surfactant is dissolved in the tin ash hydrosol；
(2) glucide and small flake diameter graphene oxide are added, and continuously stirred, obtain uniform presoma disperse system；
(3) presoma disperse system is carried out hydrothermal treatment consists, produce black precipitate；
(4) black precipitate is dried with calcination processing after, obtain Graphene and be partly coated with tin oxide nano particles
Cluster composite.
As preferred technical scheme, the concentration of the described tin ash hydrosol in step (1) is 1～200g/L,
A diameter of the 2～100nm of contained stannic oxide particle.
As preferred technical scheme, the described surfactant in step (1) be cationic ion surfactant,
One or more in anion surfactant or nonionic surfactant, described surfactant and tin ash water
The mass ratio of the stannic oxide particle in colloidal sol is 0.01～20:1.
As further preferred technical scheme, described surfactant uses the form of solution to add, table in solution
The concentration of face activating agent is 0.5～200g/L.
As preferred technical scheme, described surfactant selected from P123, F127, dodecyl sodium sulfate, 12
One or more in sodium alkyl benzene sulfonate, polyacrylamide, stearate or aliphatic alcohol sulfate.
As preferred technical scheme, the described glucide in step (2) gathers selected from glucose, sucrose, starch, shell
In the tin ash hydrosol in one or more in sugar or sodium alginate, the quality of described glucide and step (1)
The mass ratio of contained stannic oxide particle is 0.5～50:1.
As further preferred technical scheme, described glucide uses the form of solution to add, concentration be 1～
500g/L。
As in preferred technical scheme, the quality of the described small flake diameter graphene oxide in step (2) and step (1)
The tin ash hydrosol in the mass ratio of contained stannic oxide particle be 0.05～1:1, small flake diameter graphene oxide
A diameter of 200～1000nm.
As further preferred technical scheme, small flake diameter graphene oxide uses the form of aqueous dispersions to add, moisture
The concentration dissipating liquid is 0.2～50g/L.
As further preferred technical scheme, in described step (2), the continuously stirred time is 0.1～48h.
In the tin ash hydrosol, add surfactant, the spontaneous assembling of tin oxide nano particles in colloidal sol can be promoted
For Cluster Structures；After adding glucide and graphene oxide, owing to the organic molecule added is with great amount of hydroxy group, carboxylic
Base functional group, can promote the hydrogen bond between graphene oxide and tin ash cluster as bridging molecules in next step water-heat process
Formed, thus realize the Graphene cladding to tin ash cluster in end product further, due to the graphite oxide used
Alkene is small flake diameter, and therefore in end product, Graphene forms half clad structure to tin ash cluster, as lithium ion battery/sodium
During the negative material of ion battery, leave the transmission channel of lithium/sodium ion.
As preferred technical scheme, the temperature of the described hydrothermal treatment consists in step (3) is 110～200 DEG C, during process
Between be 1～50h.
Series reaction is there is in presoma disperse system in the hydro-thermal reaction of High Temperature High Pressure, including: graphene oxide is at sugar
It is partially reduced under class material reduction, loses surface oxygen functional group, π-π stacking occurs under π key effect, to titanium dioxide
Stannum cluster forms coating function；Meanwhile, glucide decomposes under high-temperature high-voltage reaction, is changed into amorphous carbon, in group
The nanosphere cladding that stannic oxide particle and surfactant molecule are formed by bunch inside is got up, and plays firm cluster internal structure
Effect.
As preferred technical scheme, the dried in described step (4) uses freeze-drying, treatment temperature
For-100～0 DEG C, processing pressure is 0～100Pa.
As preferred technical scheme, the temperature of the described calcination processing in step (4) is 400～600 DEG C, during process
Between be 0.5～20h.
Freeze-drying avoids the surface tension effects of water in drying course, can the micro-knot in inside of preferably reserved materials
Structure, prevents structure collapses.In calcination process, the Graphene in material is reduced sufficiently, and electric conductivity improves further；In cluster
The saccharide residue in portion also obtains abundant carbonization, and surfactant decomposes simultaneously, leaves the pore space structure of Nano grade.
Compared with prior art, the stannic oxide particle in the product that the preparation method that the present invention provides obtains has less
More homogeneous particle diameter, and form porous clusters structure, at the inside and outside bilayer having amorphous carbon and Graphene respectively of cluster
Clad structure.This special construction effectively slow down generating and its loss to active substance of SEI layer, and makes material have
More preferably while electric conductivity, three-D nano-porous structure and half clad structure of Graphene in cluster can make it for lithium
During the negative material of ion battery/sodium-ion battery, lithium/sodium ion more effectively and promptly embeds and deviates from.As lithium from
When sub-cell negative electrode material carries out discharge and recharge, under the big electric current of material, discharge and recharge has the specific volume of up to 800mAh/g after repeatedly circulating
Amount.
The material with carbon element such as tin ash and Graphene is combined by the present invention, is effectively improved material electric conductivity, utilizes graphite simultaneously
The special construction of alkene constructs three-dimensional porous composite, in conjunction with the nano-scale of stannic oxide particle itself, more effectively improves
Lithium/sodium ion, in the efficiency of transmission within electrode material, improves material performance under big electric current during discharge and recharge.
Accompanying drawing explanation
Fig. 1 is that the present invention prepares composite as scanning electron during lithium ion battery/sodium ion battery electrode material
Microphotograph；
Fig. 2 is that composite prepared by the present invention is electric as transmission during lithium ion battery/sodium ion battery electrode material
Sub-microphotograph.
Detailed description of the invention
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings, and described embodiment is with the technology of the present invention
Implement under premised on scheme, give detailed embodiment and concrete operating process, but protection scope of the present invention
It is not limited to following embodiment.
Embodiment 1
The preparation method of the tin oxide nano particles cluster composite of a kind of Graphene half cladding, including following step
Rapid:
(1st) step, under stirring, is dissolved in surfactant in the tin ash hydrosol, specifically comprise the following steps that by
The hydrosol of the tin oxide nano particles containing a diameter of 2nm is diluted to 20g/L, takes 20mL, under stirring wherein
Adding 0.5g surfactant P123, stirring makes it dissolve.
(2nd) step, adds glucide and the aqueous dispersions of small flake diameter graphene oxide, and continuously stirred, obtains uniformly
Presoma disperse system, specifically comprise the following steps that adding concentration is the glucose solution 2mL of 200g/L, being subsequently added concentration is
The aqueous dispersions 4mL of the small flake diameter graphene oxide (a diameter of the 200 of small flake diameter graphene oxide～1000nm) of 10g/L, and
Continuously stirred 2h.
(3rd) step, carries out high-temperature water heat treatment by presoma disperse system obtained in the previous step, produces black precipitate, tool
Body step is as follows: sealed by presoma disperse system, is placed in 180 DEG C of hot environments holding 6h, produces black precipitate.
(4th) step, by product lyophilization obtained in the previous step, and calcines；Specifically comprise the following steps that hydrothermal treatment consists
After the black precipitate lyophilization that obtains, temperature is-50 DEG C, and air pressure is 10Pa；Subsequently the product that lyophilization obtains is existed
Calcining under 500 DEG C of environment, the time is 4h.
The tin oxide nano particles cluster composite of the Graphene obtained half cladding is characterized, such as the scanning electricity of Fig. 1
Shown in sub-microphotograph, there it can be seen that the tin oxide nano particles cluster that the Graphene half that the present invention prepares is coated with
Tin ash cluster size in composite is 0.2～5 μm, and Graphene forms half clad structure to tin ash cluster；As
Shown in the transmission electron microscope photo of Fig. 2, the tin oxide nano particles cluster of the graphene coated that the present invention prepares is combined
Tin oxide nano particles size in material is about 5nm, and cluster Hole size is about 7～8nm；The graphite that the present invention prepares
Alkene half cladding tin oxide nano particles cluster composite when carrying out discharge and recharge as lithium ion battery negative material,
There is after 500 circulations of discharge and recharge under the big electric current of 1000mA/g the height ratio capacity of 800mAh/g.
Embodiment 2
Graphene half cladding tin oxide nano particles cluster composite material and preparation method thereof, comprises the following steps:
(1st) step, under stirring, is dissolved in surfactant in the tin ash hydrosol, specifically comprise the following steps that by
The hydrosol of the tin oxide nano particles containing a diameter of 5nm is diluted to 1g/L, takes 400mL, under stirring wherein
Adding 5g surfactant polyacrylamide, stirring makes it dissolve.
(2nd) step, adds glucide and the aqueous dispersions of small flake diameter graphene oxide, and continuously stirred, obtains uniformly
Presoma disperse system, specifically comprise the following steps that adding concentration is the sodium alginate soln 500mL of 2g/L, being subsequently added concentration is
The aqueous dispersions 100mL of the small flake diameter graphene oxide (a diameter of the 200 of small flake diameter graphene oxide～1000nm) of 0.2g/L,
And continuously stirred 0.5h.
(3rd) step, carries out high-temperature water heat treatment by presoma disperse system, produces black precipitate, specifically comprise the following steps that by
Presoma disperse system seals, and is placed in 200 DEG C of hot environments holding 48h, produces black precipitate.
(4th) step, by black precipitate lyophilization obtained in the previous step, and calcines, specifically comprises the following steps that step
Suddenly the black precipitate lyophilization obtained after (3) hydro-thermal, temperature is-10 DEG C, and air pressure is 20Pa；Subsequently lyophilization is obtained
Product calcine under 400 DEG C of environment, the time is 2h.When carrying out discharge and recharge as lithium ion battery negative material,
There is after 500 circulations of discharge and recharge under the big electric current of 1000mA/g the specific capacity of 750mAh/g.
Embodiment 3
The tin oxide nano particles cluster lithium ion battery/sodium ion battery electrode material of a kind of Graphene half cladding
Preparation method, comprises the following steps:
(1st) step, under stirring, is dissolved in surfactant in the tin ash hydrosol, specifically comprise the following steps that by
The hydrosol of the tin oxide nano particles containing a diameter of 10nm is diluted to 50g/L, takes 8mL, under stirring wherein
Add P123, F127, dodecyl sodium sulfate, dodecylbenzene sodium sulfonate, polyacrylamide, stearate or fatty alcohol sulphuric acid
One or more in salt, the present embodiment selects to add 1g surfactant F127, and stirring makes it dissolve.
(2nd) step, adds glucide and the aqueous dispersions of small flake diameter graphene oxide, and continuously stirred, obtains uniformly
Presoma disperse system, specifically comprise the following steps that adding concentration is the chitosan solution 50mL of 20g/L, being subsequently added concentration is
The aqueous dispersions 10mL of the small flake diameter graphene oxide (a diameter of the 200 of small flake diameter graphene oxide～1000nm) of 40g/L, and
Continuously stirred 12h, obtains uniform presoma disperse system.
(3rd) step, carries out high-temperature water heat treatment by presoma disperse system, produces black precipitate, specifically comprise the following steps that by
Presoma disperse system seals, and is placed in 150 DEG C of hot environments holding 12h, produces black precipitate.
(4th) step, by product lyophilization obtained in the previous step, and calcines, specifically comprises the following steps that step (3)
The black precipitate lyophilization obtained after hydro-thermal, temperature is-70 DEG C, and air pressure is 5Pa；The product subsequently lyophilization obtained
Calcining under 550 DEG C of environment, the time is 10h.When carrying out discharge and recharge as lithium ion battery negative material, 1000mA/g's
There is after 1000 circulations of discharge and recharge under big electric current the specific capacity of 780mAh/g.
Embodiment 4
The tin oxide nano particles cluster lithium ion battery/sodium ion battery electrode material of a kind of Graphene half cladding
Preparation method, comprises the following steps:
(1st) step, under stirring, is dissolved in surfactant in the tin ash hydrosol, specifically comprise the following steps that by
The hydrosol of the tin oxide nano particles containing a diameter of 50nm is diluted to 200g/L, takes 2mL, under stirring wherein
Adding 0.05g surfactant sodium dodecyl base sodium sulfonate, stirring makes it dissolve.
(2nd) step, adds glucide and the aqueous dispersions of small flake diameter graphene oxide, and continuously stirred, obtains uniformly
Presoma disperse system, specifically comprise the following steps that adding concentration in the mixed solution that step (1) obtains is that the sucrose of 500g/L is molten
Liquid 0.5mL, be subsequently added small flake diameter graphene oxide that concentration is 50g/L (small flake diameter graphene oxide a diameter of 200～
Aqueous dispersions 0.5mL 1000nm), and continuously stirred 48h, obtain uniform presoma disperse system.
(3rd) step, carries out high-temperature water heat treatment by presoma disperse system, produces black precipitate, specifically comprise the following steps that by
Presoma disperse system seals, and is placed in 110 DEG C of hot environments holding 2h.
(4th) step, by black precipitate lyophilization obtained in the previous step, and calcines, specifically comprises the following steps that step
Suddenly the black precipitate lyophilization obtained after (3) hydro-thermal, temperature is-100 DEG C, and air pressure is 5Pa；Subsequently lyophilization is obtained
Product calcine under 600 DEG C of environment, the time is 20h.When carrying out discharge and recharge as lithium ion battery negative material,
There is after 500 circulations of discharge and recharge under the big electric current of 1000mA/g the specific capacity of 820mAh/g.
Embodiment 5
(1st) step, under stirring, is dissolved in surfactant in the tin ash hydrosol, specifically comprises the following steps that and take
A certain amount of containing 1～200g/L, a diameter of 2～the hydrosol of the tin oxide nano particles of 100nm, under stirring,
Add P123, F127, dodecyl sodium sulfate, dodecylbenzene sodium sulfonate, polyacrylamide, stearate or fatty alcohol sulphuric acid
One or more in salt, and to make the quality of surfactant be that in the tin ash hydrosol, tin ash mass ratio is 0.01
～20:1, the present embodiment selects the surfactant added to be the mass mixing such as P123 and F127.
(2nd) step, adds glucide and the aqueous dispersions of small flake diameter graphene oxide, and continuously stirred, obtains uniformly
Presoma disperse system, specifically comprise the following steps that the glucide of addition is selected from glucose, sucrose, starch, chitosan or alginic acid
One or more in sodium, and use the form of its aqueous solution to add, the concentration of aqueous solution is 1～500g/L, it is ensured that saccharide thing
Contained tin ash mass ratio is 0.5～50:1 to the quality of matter with the tin ash hydrosol, and small flake diameter graphene oxide uses
Its aqueous dispersions, concentration is 0.2～50g/L, a diameter of 200～1000nm, the quality of small flake diameter graphene oxide and titanium dioxide
In the stannum hydrosol, contained tin ash mass ratio is 0.05～1:1, adds glucide and the moisture of small flake diameter graphene oxide
After dissipating liquid, continuously stirred 0.1～48h, obtain uniform presoma disperse system.The present embodiment selects glucide to be sucrose and shell
Polysaccharide 1:1 in mass ratio mixes.
(3rd) step, carries out high-temperature water heat treatment by presoma disperse system, produces black precipitate, specifically comprise the following steps that by
Presoma disperse system seals, and is placed in hydro-thermal reaction 1～50h at a temperature of 110～200 DEG C, produces black precipitate.
(4th) step, is dried black precipitate obtained in the previous step, and calcines, specifically comprise the following steps that step
(3) black precipitate obtained after hydro-thermal uses freeze-drying to be dried, and condition is-100～0 DEG C, and 0～100Pa；Subsequently by cold
Freeze the product being dried to obtain under 400～600 DEG C of environment, calcine 0.5～20h, obtain Graphene half cladding stannic oxide nanometer
Grain cluster composite.
The composite that the present embodiment obtains is for the negative material of lithium ion battery/sodium-ion battery, under big electric current
There is more high power capacity, there is more preferable charge and discharge circulation life simultaneously.
Claims (9)
1. a Graphene half cladding tin oxide nano particles cluster composite material and preparation method thereof, it is characterised in that include with
Lower step:
(1), under stirring, surfactant is dissolved in the tin ash hydrosol；
(2) glucide and small flake diameter graphene oxide are added, and continuously stirred, obtain uniform presoma disperse system；
(3) presoma disperse system is carried out hydrothermal treatment consists, produce black precipitate；
(4) black precipitate is dried with calcination processing after, obtain Graphene half cladding tin oxide nano particles cluster
Composite.
Graphene the most according to claim 1 half cladding tin oxide nano particles cluster composite material and preparation method thereof, its
Being characterised by, the concentration of the described tin ash hydrosol in step (1) is 1～200g/L, contained stannic oxide particle
A diameter of 2～100nm.
Graphene the most according to claim 1 half cladding tin oxide nano particles cluster composite material and preparation method thereof, its
Be characterised by, the described surfactant in step (1) be cationic ion surfactant, anion surfactant or
One or more in nonionic surfactant, described surfactant and the tin ash in the tin ash hydrosol
The mass ratio of grain is 0.01～20:1.
4. according to the Graphene described in claim 1 or 3 half cladding tin oxide nano particles cluster composite material and preparation method thereof,
It is characterized in that, described surfactant selected from P123, F127, dodecyl sodium sulfate, dodecylbenzene sodium sulfonate, poly-third
One or more in acrylamide, stearate or aliphatic alcohol sulfate.
Graphene the most according to claim 1 half cladding tin oxide nano particles cluster composite material and preparation method thereof, its
Being characterised by, the described glucide in step (2) is selected from glucose, sucrose, starch, chitosan or sodium alginate
Plant or multiple, the stannic oxide particle that the quality of described glucide is contained with the tin ash hydrosol in step (1)
Mass ratio be 0.5～50:1.
Graphene the most according to claim 1 half cladding tin oxide nano particles cluster composite material and preparation method thereof, its
It is characterised by, in the tin ash hydrosol in the quality of the described small flake diameter graphene oxide in step (2) and step (1)
The mass ratio of contained stannic oxide particle is 0.05～1:1, a diameter of the 200 of small flake diameter graphene oxide～1000nm.
Graphene the most according to claim 1 half cladding tin oxide nano particles cluster composite material and preparation method thereof, its
Being characterised by, the temperature of the described hydrothermal treatment consists in step (3) is 110～200 DEG C, and the process time is 1～50h.
Graphene the most according to claim 1 half cladding tin oxide nano particles cluster composite material and preparation method thereof, its
Being characterised by, the dried in described step (4) uses freeze-drying, and treatment temperature is-100～0 DEG C, processing pressure
It is 0～100Pa.
Graphene the most according to claim 1 half cladding tin oxide nano particles cluster composite material and preparation method thereof, its
Being characterised by, the temperature of the described calcination processing in step (4) is 400～600 DEG C, and the process time is 0.5～20h.
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| CN107240682B (en) * | 2017-05-27 | 2020-07-03 | 广东烛光新能源科技有限公司 | Lithium titanate negative electrode material and preparation method thereof |
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| CN113571707A (en) * | 2021-07-23 | 2021-10-29 | 青岛农业大学 | Preparation and application of carbon-coated tin dioxide nanoparticles |
| CN114113238A (en) * | 2021-11-17 | 2022-03-01 | 中国兵器工业集团第二一四研究所苏州研发中心 | Gas sensor based on three-dimensional porous graphene @ quantum dot composite material and preparation method thereof |
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