CN109603699A - A kind of limited hydrothermal system preparation MnCO3The method of@RF hollow compound microsphere - Google Patents
A kind of limited hydrothermal system preparation MnCO3The method of@RF hollow compound microsphere Download PDFInfo
- Publication number
- CN109603699A CN109603699A CN201910006484.3A CN201910006484A CN109603699A CN 109603699 A CN109603699 A CN 109603699A CN 201910006484 A CN201910006484 A CN 201910006484A CN 109603699 A CN109603699 A CN 109603699A
- Authority
- CN
- China
- Prior art keywords
- mnco
- dumbbell shaped
- manganese carbonate
- microsphere
- deionized water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
Abstract
The present invention relates to a kind of limited hydrothermal systems to prepare MnCO3The method of@RF hollow compound microsphere, preparation process are divided into three steps: the hydrothermal synthesis of dumbbell shaped manganese carbonate, phenolic aldehyde cladding prepare core-shell structure MnCO3Synthesis MnCO under@RF complex microsphere, limited hydrothermal condition3@RF hollow compound microsphere.Wherein, being limited the synthesis of (cladding of phenolic aldehyde layer) hydrothermal system is crucial, the formation of decision complex microsphere hollow structure, while not doing the addition of any chemical agent during being somebody's turn to do, only by MnCO3@RF complex microsphere disperses in aqueous solution.The presence of phenolic aldehyde layer guarantees the formation of hollow structure, improves the electric conductivity of manganese carbonate microballoon, inhibits the volume change of manganese carbonate in use.Hollow structure can also buffer the volume change of manganese carbonate.MnCO3The substance for having larger harm to environment is not used in@RF hollow compound microsphere mature preparation process in the process, and raw material is easy to get, and while as lithium ion battery negative material, also has potential application value in fields such as environmentology, biological medicines.
Description
Technical field
The invention belongs to nucleocapsid composite microsphere material field, it is related to a kind of limited hydrothermal system preparation MnCO3@RF is hollow
The method of complex microsphere.
Background technique
Currently, the excessive use due to traditional fuel causes serious problem of environmental pollution, thus as can be recycled,
The lithium ion battery of the lower secondary cell of environmental hazard is got growing concern for.As the important of lithium ion battery
Component part, negative electrode material have vital influence to the performance of battery.However commercial Li-ion battery negative electrode material
Always based on theoretical capacity lower (372mAh/g) and the poor carbon-based material such as graphene of cycle performance.To improve lithium ion
The performance of battery, with manganese carbonate (MnCO3) it is the transition metal carbonate of representative as novel cathode material for lithium ion battery
Research deepens continuously.Manganese carbonate theoretical capacity with higher (> 1000mAh/g), cycle performance is preferable.But manganese carbonate is also deposited
Electric conductivity is poor, charge/discharge during volume change it is larger the problems such as.The effective way solved these problems is by manganese carbonate
With the compound comprehensive performance to improve manganese carbonate of other materials.Wang Jing etc. (CN201510621387.7) is prepared doped with carbon
The manganese carbonate complex microsphere of sour nickel, wherein nickelous carbonate and manganese carbonate molar ratio are 1:100~30:100, and discharge capacity reaches for the first time
1500mAh/g, capacity is still higher than 500mAh/g after recycling 100 times.Carbon is prepared in Huang little Xiao etc. (CN 201710408312.X)
Sour manganese/ferroso-ferric oxide/graphene trielement composite material, capacity is after recycling 1000 times under the current density of 1000mA/g
532mAh g-1.Zhang Jianxins etc. (CN201610333350.9) are prepared in situ to obtain carbon coating manganese carbonate microballoon by one-step method,
The current density initial capacity of 100mA/g is 998mAh g-1, capacity is 430mAh g after recycling 100 times-1.Although current carbonic acid
Manganese composite material complex form multiplicity, but there is not yet hollow MnCO is prepared under limited (cladding of phenolic aldehyde layer) hydrothermal system3@
The report of RF complex microsphere.
Summary of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes a kind of limited hydrothermal system preparation MnCO3@RF is hollow
The method of complex microsphere.
Technical solution
A kind of limited hydrothermal system preparation MnCO3The method of@RF hollow compound microsphere, it is characterised in that steps are as follows:
Step 1: anhydrous Manganese chloride, urea, two citric acid monohydrate trisodiums, Sodium Polyacrylate are mixed;
The anhydrous Manganese chloride, urea, trisodium citrate dihydrate, Sodium Polyacrylate mass ratio be 1:1.6~1.7:5~
5.2:0.9~1.0;
The Sodium Polyacrylate molecular weight is 800-1000 ten thousand;
The mass concentration of the anhydrous Manganese chloride is 7.8-8.0kg/m3;
Step 2: deionized water is added, is placed on magnetic stirring apparatus and opens stirring, heating makes it completely dissolved;
Step 3: being cooled to room temperature, transfer the solution into stainless steel-polytetrafluoroethyllining lining autoclave and put
Enter baking oven, set temperature is 170~180 DEG C, 5~6h of insulation reaction;It is cooled to room temperature, wash, be centrifugated through deionized water,
It is freeze-dried up to dumbbell shaped manganese carbonate MnCO3;
Step 4: by dumbbell shaped manganese carbonate and resorcinol, disperses and be dissolved in the mixed solution of second alcohol and water, ultrasound
5min or more obtains suspension;
The dumbbell shaped MnCO3 withThe mass ratio of resorcinol is 1:5~6;
The volume ratio of water and ethyl alcohol is 1:1.8~2 in the mixed solution;
The mass concentration of the dumbbell shaped manganese carbonate is 0.8-1.0kg/m3;
Step 5: stirring suspension when temperature is 25~35 DEG C, it is water-soluble to add the formaldehyde that mass fraction is 37~40%
After stirring 20~40min, the ammonium hydroxide that mass fraction is 25% is added in liquid;8~12h of isothermal reaction, products therefrom is through dehydrated alcohol
Cleaning, centrifuge separation, vacuum drying treatment are to get dumbbell shaped MnCO3@RF complex microsphere, wherein RF is phenolic aldehyde;
The mass ratio of the dumbbell shaped manganese carbonate and formalin is 1:6~7;
The mass ratio of the dumbbell shaped manganese carbonate and ammonium hydroxide is 1:35~40;
Step 6: weighing dumbbell shaped MnCO obtained3@RF complex microsphere, which is dispersed in deionized water, obtains suspension,
And be transferred into stainless steel-polytetrafluoroethyllining lining autoclave, it is placed in baking oven, set temperature is 200~220
DEG C, keep the temperature 24~36h;Wherein MnCO3The mass concentration of@RF is 1.5-2.0kg/m3;
Step 7: autoclave being cooled to room temperature, product is centrifuged, is freeze-dried up to MnCO3@RF is hollow
Complex microsphere.
The water uses deionized water.
The ethyl alcohol uses dehydrated alcohol.
The speed of agitator of the step 5 is 300~500rpm.
Beneficial effect
A kind of limited hydrothermal system proposed by the present invention prepares MnCO3The method of@RF hollow compound microsphere, preparation process point
Core-shell structure MnCO is prepared for three steps: the hydrothermal synthesis of dumbbell shaped manganese carbonate, phenolic aldehyde cladding3@RF complex microsphere, limited hydro-thermal item
Synthesis MnCO under part3@RF hollow compound microsphere.Wherein, being limited the synthesis of (cladding of phenolic aldehyde layer) hydrothermal system is key, certainly
Determine the formation of complex microsphere hollow structure, while the addition of any chemical agent should not done in the process, only by MnCO3@RF is compound
Microballoon disperses in aqueous solution.The presence of phenolic aldehyde layer guarantees the formation of hollow structure, improves the electric conductivity of manganese carbonate microballoon,
Inhibit the volume change of manganese carbonate in use.Hollow structure can also buffer the volume change of manganese carbonate.MnCO3@RF
The substance for having larger harm to environment is not used in hollow compound microsphere mature preparation process in the process, and raw material is easy to get, as lithium
While ion battery cathode material, also there is potential application value in fields such as environmentology, biological medicines.
Detailed description of the invention
Fig. 1 is the SEM photograph of dumbbell shaped manganese carbonate
Fig. 2 is dumbbell shaped MnCO3The TEM photo of@RF complex microsphere
Fig. 3 is dumbbell shaped MnCO3The TEM and SEM photograph of@RF hollow compound microsphere
Fig. 4 is dumbbell shaped MnCO3The XRD spectra of@RF hollow compound microsphere
Specific embodiment
Now in conjunction with embodiment, attached drawing, the invention will be further described:
1 dumbbell shaped MnCO of embodiment3@RF hollow compound microsphere
Weigh anhydrous Manganese chloride 0.52g, urea 0.84g, two citric acid monohydrate trisodiums 2.60g, Sodium Polyacrylate (molecular weight
It is 800-1000 ten thousand) 0.52g in beaker, 65mL deionized water is added into beaker, is placed on magnetic stirring apparatus and opens and stir
It mixes, heating makes it completely dissolved, and transfers the solution into stainless steel-polytetrafluoroethyllining lining autoclave and puts after cooling
Enter baking oven, set temperature is 170 DEG C, takes out, is cooled to room temperature after insulation reaction 5h, through deionized water washing, is centrifugated, cold
Jelly is drying to obtain dumbbell shaped manganese carbonate;Dumbbell shaped manganese carbonate 0.32g, resorcinol 1.92g are weighed, disperses, be dissolved in 350mL second
Alcohol solution (dehydrated alcohol, deionized water volume ratio be 2:1) in, ultrasonic 5min or more obtains suspension, suspension is added
In there-necked flask containing stirring, stirring is opened, setting revolving speed is 400rpm, and reaction temperature is set as 30 DEG C;It is by mass fraction
37~40% formalin 2.24g is added in there-necked flask, after stirring 30min, the ammonium hydroxide for being 25% by mass fraction
11.20g is added in there-necked flask, and isothermal reaction 8h, product is through washes of absolute alcohol, centrifuge separation, vacuum drying treatment to get mute
Bell-shaped MnCO3@RF complex microsphere (RF is phenolic aldehyde);Weigh dumbbell shaped MnCO obtained3@RF complex microsphere 0.13g is dispersed in
Suspension is obtained in 65mL deionized water, and is transferred into stainless steel-polytetrafluoroethyllining lining autoclave, is placed in
Baking oven, set temperature are 200 DEG C, and heat preservation is for 24 hours;Autoclave is cooled to room temperature, product is centrifuged, freeze-drying i.e.
Obtain MnCO3@RF hollow compound microsphere.
2 dumbbell shaped MnCO of embodiment3@RF hollow compound microsphere
Weigh anhydrous Manganese chloride 0.56g, urea 0.90g, two citric acid monohydrate trisodiums 2.80g, Sodium Polyacrylate (molecular weight
It is 800-1000 ten thousand) 0.56g in beaker, 70mL deionized water is added into beaker, is placed on magnetic stirring apparatus and opens and stir
It mixes, heating makes it completely dissolved, and transfers the solution into stainless steel-polytetrafluoroethyllining lining autoclave and puts after cooling
Enter baking oven, set temperature is 170 DEG C, takes out, is cooled to room temperature after insulation reaction 6h, through deionized water washing, is centrifugated, cold
Jelly is drying to obtain dumbbell shaped manganese carbonate;Dumbbell shaped manganese carbonate 0.36g, resorcinol 2.16g are weighed, disperses, be dissolved in 400mL second
Alcohol solution (dehydrated alcohol, deionized water volume ratio be 2:1) in, ultrasonic 5min or more obtains suspension, suspension is added
In there-necked flask containing stirring, stirring is opened, setting revolving speed is 400rpm, and reaction temperature is set as 30 DEG C;It is by mass fraction
37~40% formalin 2.52g is added in there-necked flask, after stirring 30min, the ammonium hydroxide for being 25% by mass fraction
12.60g is added in there-necked flask, and isothermal reaction 8h, product is through washes of absolute alcohol, centrifuge separation, vacuum drying treatment to get mute
Bell-shaped MnCO3@RF complex microsphere (RF is phenolic aldehyde);Weigh dumbbell shaped MnCO obtained3@RF complex microsphere 0.14g is dispersed in
Suspension is obtained in 70mL deionized water, and is transferred into stainless steel-polytetrafluoroethyllining lining autoclave, is placed in
Baking oven, set temperature are 200 DEG C, and heat preservation is for 24 hours;Autoclave is cooled to room temperature, product is centrifuged, freeze-drying i.e.
Obtain MnCO3@RF hollow compound microsphere.
3 dumbbell shaped MnCO of embodiment3@RF hollow compound microsphere
Weigh anhydrous Manganese chloride 0.60g, urea 0.96g, two citric acid monohydrate trisodiums 3.00g, Sodium Polyacrylate (molecular weight
It is 800-1000 ten thousand) 0.60g in beaker, 70mL deionized water is added into beaker, is placed on magnetic stirring apparatus and opens and stir
It mixes, heating makes it completely dissolved, and transfers the solution into stainless steel-polytetrafluoroethyllining lining autoclave and puts after cooling
Enter baking oven, set temperature is 180 DEG C, takes out, is cooled to room temperature after insulation reaction 5h, through deionized water washing, is centrifugated, cold
Jelly is drying to obtain dumbbell shaped manganese carbonate;Dumbbell shaped manganese carbonate 0.41g, resorcinol 2.46g are weighed, disperses, be dissolved in 450mL second
Alcohol solution (dehydrated alcohol, deionized water volume ratio be 2:1) in, ultrasonic 5min or more obtains suspension, suspension is added
In there-necked flask containing stirring, stirring is opened, setting revolving speed is 400rpm, and reaction temperature is set as 30 DEG C;It is by mass fraction
37~40% formalin 2.87g is added in there-necked flask, after stirring 30min, the ammonium hydroxide for being 25% by mass fraction
14.35g be added there-necked flask in, isothermal reaction 10h, product through washes of absolute alcohol, centrifuge separation, vacuum drying treatment to get
Dumbbell shaped MnCO3@RF complex microsphere (RF is phenolic aldehyde);Weigh dumbbell shaped MnCO obtained3@RF complex microsphere 0.15g is evenly dispersed
Suspension is obtained in 75mL deionized water, and is transferred into stainless steel-polytetrafluoroethyllining lining autoclave, is set
In baking oven, set temperature is 210 DEG C, keeps the temperature 28h;Autoclave is cooled to room temperature, product is centrifuged, is freeze-dried
Up to MnCO3@RF hollow compound microsphere.
4 dumbbell shaped MnCO of embodiment3@RF hollow compound microsphere
Weigh anhydrous Manganese chloride 0.64g, urea 1.03g, two citric acid monohydrate trisodiums 3.20g, Sodium Polyacrylate (molecular weight
It is 800-1000 ten thousand) 0.64g in beaker, 80mL deionized water is added into beaker, is placed on magnetic stirring apparatus and opens and stir
It mixes, heating makes it completely dissolved, and transfers the solution into stainless steel-polytetrafluoroethyllining lining autoclave and puts after cooling
Enter baking oven, set temperature is 180 DEG C, takes out, is cooled to room temperature after insulation reaction 6h, through deionized water washing, is centrifugated, cold
Jelly is drying to obtain dumbbell shaped manganese carbonate;Dumbbell shaped manganese carbonate 0.45g, resorcinol 2.70g are weighed, disperses, be dissolved in 500mL second
Alcohol solution (dehydrated alcohol, deionized water volume ratio be 2:1) in, ultrasonic 5min or more obtains suspension, suspension is added
In there-necked flask containing stirring, stirring is opened, setting revolving speed is 400rpm, and reaction temperature is set as 30 DEG C;It is by mass fraction
37~40% formalin 3.15g is added in there-necked flask, after stirring 30min, the ammonium hydroxide for being 25% by mass fraction
15.75g be added there-necked flask in, isothermal reaction 10h, product through washes of absolute alcohol, centrifuge separation, vacuum drying treatment to get
Dumbbell shaped MnCO3@RF complex microsphere (RF is phenolic aldehyde);Weigh dumbbell shaped MnCO obtained3@RF complex microsphere 0.16g is evenly dispersed
Suspension is obtained in 80mL deionized water, and is transferred into stainless steel-polytetrafluoroethyllining lining autoclave, is set
In baking oven, set temperature is 210 DEG C, keeps the temperature 28h;Autoclave is cooled to room temperature, product is centrifuged, is freeze-dried
Up to MnCO3@RF hollow compound microsphere.
5 dumbbell shaped MnCO of embodiment3@RF hollow compound microsphere
Weigh anhydrous Manganese chloride 0.68g, urea 1.09g, two citric acid monohydrate trisodiums 3.40g, Sodium Polyacrylate (molecular weight
It is 800-1000 ten thousand) 0.68g in beaker, 85mL deionized water is added into beaker, is placed on magnetic stirring apparatus and opens and stir
It mixes, heating makes it completely dissolved, and transfers the solution into stainless steel-polytetrafluoroethyllining lining autoclave and puts after cooling
Enter baking oven, set temperature is 175 DEG C, takes out, is cooled to room temperature after insulation reaction 5h, through deionized water washing, is centrifugated, cold
Jelly is drying to obtain dumbbell shaped manganese carbonate;Dumbbell shaped manganese carbonate 0.50g, resorcinol 3.00g are weighed, disperses, be dissolved in 550mL second
Alcohol solution (dehydrated alcohol, deionized water volume ratio be 2:1) in, ultrasonic 5min or more obtains suspension, suspension is added
In there-necked flask containing stirring, stirring is opened, setting revolving speed is 400rpm, and reaction temperature is set as 30 DEG C;It is by mass fraction
37~40% formalin 3.50g is added in there-necked flask, after stirring 30min, the ammonium hydroxide for being 25% by mass fraction
17.50g be added there-necked flask in, isothermal reaction 12h, product through washes of absolute alcohol, centrifuge separation, vacuum drying treatment to get
Dumbbell shaped MnCO3@RF complex microsphere (RF is phenolic aldehyde);Weigh dumbbell shaped MnCO obtained3@RF complex microsphere 0.17g is evenly dispersed
Suspension is obtained in 85mL deionized water, and is transferred into stainless steel-polytetrafluoroethyllining lining autoclave, is set
In baking oven, set temperature is 220 DEG C, keeps the temperature 32h;Autoclave is cooled to room temperature, product is centrifuged, is freeze-dried
Up to MnCO3@RF hollow compound microsphere.
6 dumbbell shaped MnCO of embodiment3@RF hollow compound microsphere
Weigh anhydrous Manganese chloride 0.72g, urea 1.16g, two citric acid monohydrate trisodiums 3.60g, Sodium Polyacrylate (molecular weight
It is 800-1000 ten thousand) 0.72g in beaker, 90mL deionized water is added into beaker, is placed on magnetic stirring apparatus and opens and stir
It mixes, heating makes it completely dissolved, and transfers the solution into stainless steel-polytetrafluoroethyllining lining autoclave and puts after cooling
Enter baking oven, set temperature is 175 DEG C, takes out, is cooled to room temperature after insulation reaction 6h, through deionized water washing, is centrifugated, cold
Jelly is drying to obtain dumbbell shaped manganese carbonate;Dumbbell shaped manganese carbonate 0.54g, resorcinol 3.24g are weighed, disperses, be dissolved in 600mL second
Alcohol solution (dehydrated alcohol, deionized water volume ratio be 2:1) in, ultrasonic 5min or more obtains suspension, suspension is added
In there-necked flask containing stirring, stirring is opened, setting revolving speed is 400rpm, and reaction temperature is set as 30 DEG C;It is by mass fraction
37~40% formalin 3.78g is added in there-necked flask, after stirring 30min, the ammonium hydroxide for being 25% by mass fraction
18.90g be added there-necked flask in, isothermal reaction 12h, product through washes of absolute alcohol, centrifuge separation, vacuum drying treatment to get
Dumbbell shaped MnCO3@RF complex microsphere (RF is phenolic aldehyde);Weigh dumbbell shaped MnCO obtained3@RF complex microsphere 0.18g is evenly dispersed
Suspension is obtained in 90mL deionized water, and is transferred into stainless steel-polytetrafluoroethyllining lining autoclave, is set
In baking oven, set temperature is 220 DEG C, keeps the temperature 32h;Autoclave is cooled to room temperature, product is centrifuged, is freeze-dried
Up to MnCO3@RF hollow compound microsphere.
Claims (4)
1. a kind of limited hydrothermal system prepares MnCO3The method of@RF hollow compound microsphere, it is characterised in that steps are as follows:
Step 1: anhydrous Manganese chloride, urea, two citric acid monohydrate trisodiums, Sodium Polyacrylate are mixed;
The anhydrous Manganese chloride, urea, trisodium citrate dihydrate, Sodium Polyacrylate mass ratio be 1:1.6~1.7:5~5.2:
0.9~1.0;
The Sodium Polyacrylate molecular weight is 800-1000 ten thousand;
The mass concentration of the anhydrous Manganese chloride is 7.8-8.0kg/m3;
Step 2: deionized water is added, is placed on magnetic stirring apparatus and opens stirring, heating makes it completely dissolved;
Step 3: being cooled to room temperature, transfer the solution into stainless steel-polytetrafluoroethyllining lining autoclave and be put into baking
Case, set temperature are 170~180 DEG C, 5~6h of insulation reaction;It is cooled to room temperature, through deionized water washing, centrifuge separation, freezing
It is drying to obtain dumbbell shaped manganese carbonate MnCO3;
Step 4: by dumbbell shaped manganese carbonate and resorcinol, disperses and be dissolved in the mixed solution of second alcohol and water, ultrasonic 5min
More than, obtain suspension;
The dumbbell shaped MnCO3 withThe mass ratio of resorcinol is 1:5~6;
The volume ratio of water and ethyl alcohol is 1:1.8~2 in the mixed solution;
The mass concentration of the dumbbell shaped manganese carbonate is 0.8-1.0kg/m3;
Step 5: suspension is stirred when temperature is 25~35 DEG C, adds the formalin that mass fraction is 37~40%,
After stirring 20~40min, the ammonium hydroxide that mass fraction is 25% is added;8~12h of isothermal reaction, products therefrom are clear through dehydrated alcohol
It washes, be centrifugated, vacuum drying treatment is to get dumbbell shaped MnCO3@RF complex microsphere, wherein RF is phenolic aldehyde;
The mass ratio of the dumbbell shaped manganese carbonate and formalin is 1:6~7;
The mass ratio of the dumbbell shaped manganese carbonate and ammonium hydroxide is 1:35~40;
Step 6: weighing dumbbell shaped MnCO obtained3@RF complex microsphere, which is dispersed in deionized water, obtains suspension, and will
It is transferred in stainless steel-polytetrafluoroethyllining lining autoclave, is placed in baking oven, and set temperature is 200~220 DEG C, protects
24~36h of temperature;Wherein MnCO3The mass concentration of@RF is 1.5-2.0kg/m3;
Step 7: autoclave being cooled to room temperature, product is centrifuged, is freeze-dried up to MnCO3@RF Hollow Compound is micro-
Ball.
2. according to the method described in claim 1, it is characterized by: the water uses deionized water.
3. according to the method described in claim 1, it is characterized by: the ethyl alcohol uses dehydrated alcohol.
4. according to the method described in claim 1, it is characterized by: the speed of agitator of the step 5 is 300~500rpm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910006484.3A CN109603699B (en) | 2019-01-04 | 2019-01-04 | Preparation of MnCO by limited hydrothermal system3Method for @ RF hollow composite microspheres |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910006484.3A CN109603699B (en) | 2019-01-04 | 2019-01-04 | Preparation of MnCO by limited hydrothermal system3Method for @ RF hollow composite microspheres |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109603699A true CN109603699A (en) | 2019-04-12 |
CN109603699B CN109603699B (en) | 2021-07-06 |
Family
ID=66017819
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910006484.3A Active CN109603699B (en) | 2019-01-04 | 2019-01-04 | Preparation of MnCO by limited hydrothermal system3Method for @ RF hollow composite microspheres |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109603699B (en) |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120308468A1 (en) * | 2011-05-30 | 2012-12-06 | Korea Institute Of Science And Technology | Method for producing graphene by chemical exfoliation |
CN106654264A (en) * | 2017-01-12 | 2017-05-10 | 吉林大学 | Solvothermal assisted preparation method of LiFePO4/C multistage composite microspheres |
CN107275624A (en) * | 2017-07-24 | 2017-10-20 | 扬州大学 | The preparation method of carbon coating spindle shape iron oxide composite material of core-shell structure |
CN107522867A (en) * | 2017-08-31 | 2017-12-29 | 扬州大学 | The preparation method of internal confinement growth MOFs hollow Nano carbon balls |
CN108039287A (en) * | 2017-12-21 | 2018-05-15 | 齐鲁工业大学 | A kind of Fe of bivalve layer core shell structure3O4@C@MnO2Composite material and preparation method thereof |
CN108172787A (en) * | 2017-09-18 | 2018-06-15 | 浙江大学 | A kind of monodisperse hollow nano-silicon/carbon ball and its preparation method and application |
KR20180104838A (en) * | 2017-03-14 | 2018-09-27 | 주식회사 디알비동일 | Precursor for cathode active materials of core-shell structure, method for preparing the same, and cathode active materials using the same |
CN108767260A (en) * | 2018-06-05 | 2018-11-06 | 武汉理工大学 | A kind of hollow nano-electrode materials of carbon coating FeP and its preparation method and application |
CN108807943A (en) * | 2018-07-19 | 2018-11-13 | 齐鲁工业大学 | A kind of hollow-core construction CeO2@C core-shell structure copolymer nanocomposites and the preparation method and application thereof |
-
2019
- 2019-01-04 CN CN201910006484.3A patent/CN109603699B/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120308468A1 (en) * | 2011-05-30 | 2012-12-06 | Korea Institute Of Science And Technology | Method for producing graphene by chemical exfoliation |
CN106654264A (en) * | 2017-01-12 | 2017-05-10 | 吉林大学 | Solvothermal assisted preparation method of LiFePO4/C multistage composite microspheres |
KR20180104838A (en) * | 2017-03-14 | 2018-09-27 | 주식회사 디알비동일 | Precursor for cathode active materials of core-shell structure, method for preparing the same, and cathode active materials using the same |
CN107275624A (en) * | 2017-07-24 | 2017-10-20 | 扬州大学 | The preparation method of carbon coating spindle shape iron oxide composite material of core-shell structure |
CN107522867A (en) * | 2017-08-31 | 2017-12-29 | 扬州大学 | The preparation method of internal confinement growth MOFs hollow Nano carbon balls |
CN108172787A (en) * | 2017-09-18 | 2018-06-15 | 浙江大学 | A kind of monodisperse hollow nano-silicon/carbon ball and its preparation method and application |
CN108039287A (en) * | 2017-12-21 | 2018-05-15 | 齐鲁工业大学 | A kind of Fe of bivalve layer core shell structure3O4@C@MnO2Composite material and preparation method thereof |
CN108767260A (en) * | 2018-06-05 | 2018-11-06 | 武汉理工大学 | A kind of hollow nano-electrode materials of carbon coating FeP and its preparation method and application |
CN108807943A (en) * | 2018-07-19 | 2018-11-13 | 齐鲁工业大学 | A kind of hollow-core construction CeO2@C core-shell structure copolymer nanocomposites and the preparation method and application thereof |
Non-Patent Citations (2)
Title |
---|
RUIMIN XING ET AL.: ""Hydrothermal-assisted homogeneous precipitation synthesis of dumbbell-like MnCO3 nanostructures"", 《CERAMICS INTERNATIONAL》 * |
刘双科 等: ""间苯二酚–甲醛辅助溶胶–凝胶法制备纳米Li2MnSiO4/C正极材料"", 《无机材料学报》 * |
Also Published As
Publication number | Publication date |
---|---|
CN109603699B (en) | 2021-07-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102255079B (en) | Stannum-carbon composite material used for lithium ion battery cathode, preparation method thereof and lithium ion battery | |
CN105742602B (en) | A kind of sodium-ion battery cathode Sn/MoS2/ C composite and preparation method thereof | |
CN104009210B (en) | A kind of porous silicon/carbon composite material, Preparation method and use | |
CN102623693B (en) | High specific capacity spindle-shaped ferroferric oxide/carbon nano composite material for negative electrode of lithium ion battery | |
CN106960956A (en) | Modified Prussian blue material, sodium-ion battery positive plate and preparation method | |
CN106129377B (en) | A kind of preparation method of sesquioxide/graphene composite material, negative electrode of lithium ion battery, lithium ion battery | |
CN106058181A (en) | Preparation method of graphene-supported carbon-coated silicone nanoparticle composite electrode material | |
CN106340633B (en) | A kind of high performance lithium ion battery composite nano materials and preparation method thereof | |
CN108963204A (en) | Silicon substrate/sulfide cathode material preparation method of one type graphene interlayers structure | |
CN109904426B (en) | MXene induced growth nano iron oxide composite material, preparation method and application thereof | |
CN105047919B (en) | Preparation method of lithium iron phosphate battery positive electrode material | |
CN103346302A (en) | Lithium battery silicon-carbon nanotube composite cathode material as well as preparation method and application thereof | |
CN110137465A (en) | A kind of carbon@Fe2O3@carbosphere composite material and its application | |
CN107394180A (en) | Two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound silicon nanoparticle composite and preparation and application | |
CN102502789A (en) | Alkaline earth metal germanate nanomaterial and preparation method thereof and use thereof as cathode material of lithium ion battery | |
CN108270001A (en) | " one kettle way " synthesizes the preparation method of ferroso-ferric oxide@carbon composites | |
CN109473666A (en) | A kind of SbVO of graphene support4Nano particle composite material and preparation method thereof | |
CN110061239A (en) | Lignin-base binder and preparation method thereof and lithium ion battery | |
CN108183213A (en) | A kind of preparation method of di-iron trioxide/carbon/carbon nanotube lithium battery negative material | |
CN107026263A (en) | Sea urchin shape bismuth sulfide/macropore graphene composite material, preparation method and applications | |
CN106848282A (en) | A kind of negative electrode material for nonaqueous electrode secondary battery and its preparation method and application | |
CN109786690A (en) | A kind of lithium sulfur battery anode material and preparation method thereof | |
CN109494345A (en) | A kind of battery preparation method and battery promoting lithium ion battery safety performance | |
CN109037661A (en) | A kind of core-shell structure cobalt disulfide composite material and preparation method | |
CN102786048A (en) | Method for preparing conductive additive for lithium ion batteries |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |