CN109428065A - A kind of preparation method of nanometer rods composite negative pole material - Google Patents
A kind of preparation method of nanometer rods composite negative pole material Download PDFInfo
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- CN109428065A CN109428065A CN201710752019.5A CN201710752019A CN109428065A CN 109428065 A CN109428065 A CN 109428065A CN 201710752019 A CN201710752019 A CN 201710752019A CN 109428065 A CN109428065 A CN 109428065A
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation method of nanometer rods composite negative pole material, preparation process includes: the preparation of 1) ZnO nanorod；2) preparation of ZnO@silicon dioxide nano rod；3) ZnO@SiO2The preparation of@Graphene nano-rod network；4) SiO2The preparation of@graphene nano managed network totally four big process, hollow core-shell structure is presented in its composite negative pole material prepared, the conductivity of material is improved by the high mechanical property of shell graphene and high electric conductivity and reduces the expansion rate of material, the kernel silica specific surface area with higher and hollow structure formed simultaneously using layer assembly improves the transmission rate of lithium ion, and the composite negative pole material prepared is high with gram volume, imbibition liquid-keeping property is strong and its characteristics such as cycle performance is high.
Description
Technical field
The present invention relates to lithium ion battery material preparation technical field, specially a kind of system of nanometer rods composite negative pole material
Preparation Method.
Background technique
The advantages that silica negative electrode material is high, cheap with its specific capacity, and energy density is high is expected to become the next generation
Lithium ion battery negative material.Earth silicon material structure is mostly spherical or graininess at present, in use due to
The expansion rates of silicon materials is high, cause in its charge and discharge process silicon-carbon cathode due in charge and discharge process volume expansion it is larger, produce
Product are difficult to industrial application.And reducing silicon materials expansion measure mainly has: the nanosizing of material, the pore-creating of material, material are hollow
Change and its coating modification of material, but it is again simple with material village hollowing preparation process, and effect is obvious and is taken seriously.System at present
Prepared silicon dioxide hollow structure is mostly a kind of spherical, such as patent (application number: CN201310007838.9) lithium ion battery
Spherical more hollow structures are presented in the preparation method of silicon/carbon dioxide composite material, the silica prepared, and in its outer bread
One layer of carbon material is covered, although cycle performance is improved, since high rate performance is general, the reason for this is that the material of spherical structure
Contact point between material is few, causes conductivity deviation.And the silica of fibrous structure is high with its conductivity, prepared
The advantages that journey is controllable simultaneously is applied to can be improved while reducing volume dilatation in lithium ion battery negative material
The conductivity of material, the high rate performance as can be more improved its material if it coats the powerful graphene big, conductivity is high of mechanics.
Summary of the invention
Present invention solves the technical problem that being to overcome, current silica composite negative pole material conductivity is relatively low, cyclicity
The defect of energy difference etc., provides a kind of preparation method of nanometer rods composite negative pole material, to improve the high rate performance of its material
And its cycle performance.
To achieve the above object, the invention provides the following technical scheme: a kind of preparation side of nanometer rods composite negative pole material
Hollow core-shell structure is presented in method, nanometer rods composite negative pole material, and kernel is silica, and shell is the network that graphene is formed
Structure；Its detailed preparation process is as follows:
1) preparation of ZnO nanorod:
It weighs (0.2~0.4) g zinc acetate to dissolve in 60mL ethyl alcohol, while weighing (0.15~0.3) g KOH and being dissolved in 65mL second
In alcohol, two parts of solution are placed in spare (being denoted as A) at a temperature of (- 10~0) DEG C later；
It weighs (2~3) g zinc nitrate and (0.5~0.7) g hexa is dissolved in 400mL distilled water oil bath heating to 60 DEG C
Afterwards, mixed solution A is added, temperature is risen to 90 DEG C, whisks Temperature fall after 2h, centrifuge washing is drying to obtain ZnO nanorod；
2) preparation of ZnO@silicon dioxide nano rod:
The ZnO nanorod template for weighing (0.1~0.3) g is uniformly dispersed in 20mL H2O、120mL CH3CH2OH and 20mL
NH3•H2In the mixed solution of O, the positive cinnamic acid tetrem vinegar (TEOS) of 60 μ L is added dropwise in the state of whisking later, continues to pull
1h is mixed, with water and ethanol washing, is drying to obtain ZnO@silicon dioxide nano rod；
3) ZnO@SiO2The preparation of@Graphene nano-rod network:
The ZnO@silicon dioxide nano rod of 0.5g is dispersed in the NaCl aqueous solution that 60mL concentration is 0.5mol/L, is then added dropwise
0.75g diallyl dimethyl ammoniumchloride (PDDA), centrifuge washing three times, disperses 30mL for nanometer rods later after whisking 1h
In distilled water, 30mL graphene oxide dispersion (0.2g) is added dropwise in the state of whisking, continues to whisk 6h, be centrifuged three times, again
It is scattered in distilled water, NaBH is added dropwise4Solution (2g NaBH4It is dissolved in 10mL distilled water), centrifuge washing is dry；
4) preparation of SiO2@G nanotube network:
It is washed using the HC1 solution of 1mol/L, ZnO template is removed, the SiO2 nanotube of final product graphene coated is obtained
Network.
Compared with prior art, the beneficial effects of the present invention are:
1) preparing nano-hollow stick silica/graphene has the characteristics that large specific surface area, conductivity are strong, makes it in charge and discharge
In the process, its expansion rate is buffered, while improving leading for material by the high mechanical property of shell graphene and high electric conductivity again
Electric rate and reduce material expansion rate, while using layer assembly formed kernel silica specific surface area with higher and
The transmission rate of hollow structure raising lithium ion.
2) graphene/silicon dioxide nanometer rods composite negative pole material has layer assembly structure, and kernel is hollow structure, in
Interbed is silica, and shell is grapheme material, plays the wherein synergistic effect between interbed and shell, i.e. shell graphene
The feature that conductivity is high and its mechanical property is strong buffers the expansion of silica in charge and discharge process, while silica Gao Rong
The characteristics of amount and the carboxylic group for combining surface of graphene oxide, improve the combination between its silica and graphene oxide
Power forms firm graphene/silicon dioxide material.
Detailed description of the invention
Fig. 1 is silica/graphene SEM picture that the embodiment of the present invention 1 is prepared.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
Referring to Fig. 1, the present invention provides a kind of technical solution: a kind of preparation method of nanometer rods composite negative pole material, nanometer rods
Hollow core-shell structure is presented in composite negative pole material, and kernel is silica, and shell is the network structure that graphene is formed；It is in detail
Thin preparation process is as follows:
1) preparation of ZnO nanorod:
It weighs 0.3g zinc acetate to dissolve in 60mL ethyl alcohol, while weighing 0.2g KOH and being dissolved in 65mL ethyl alcohol, later by two parts
Solution is spare at a temperature of being placed in 0 DEG C (being denoted as A).
It weighs 2.5g zinc nitrate and 0.6g hexa is dissolved in 400mL distilled water oil bath heating to after 60 DEG C, add
Enter mixed solution A, temperature is risen to 90 DEG C, whisks Temperature fall after 2h, centrifuge washing is drying to obtain ZnO nanorod.
2) preparation of ZnO@silicon dioxide nano rod:
The ZnO nanorod template for weighing 0.2g is uniformly dispersed in 20mLH2O、120mL CH3CH2OH and 20mL NH3•H2O's is mixed
Close in solution, the positive cinnamic acid tetrem vinegar (TEOS) of 60 μ L be added dropwise in the state of whisking later, continues to whisk 1h, with water and
Ethanol washing is drying to obtain ZnO@silicon dioxide nano rod.
3) ZnO@SiO2The preparation of@Graphene nano-rod network:
The ZnO@silicon dioxide nano rod of 0.5g is dispersed in the NaCl aqueous solution that 60mL concentration is 0.5mol/L, is then added dropwise
0.75g diallyl dimethyl ammoniumchloride (PDDA), centrifuge washing three times, disperses 30mL for nanometer rods later after whisking 1h
In distilled water, 30mL graphene oxide dispersion (0.2g) is added dropwise in the state of whisking, continues to whisk 6h, be centrifuged three times, again
It is scattered in distilled water, NaBH is added dropwise4Solution (2gNaBH4It is dissolved in 10mL distilled water), centrifuge washing is dry.
4) SiO2The preparation of@G nanotube network:
It is washed using the HC1 solution of 1mol/L, ZnO template is removed, the SiO of final product graphene coated is obtained2Nanotube
Network.
Embodiment 2
A kind of preparation method of nanometer rods composite negative pole material, hollow core-shell structure is presented in nanometer rods composite negative pole material, interior
Core is silica, and shell is the network structure that graphene is formed；Its detailed preparation process is as follows:
1) preparation of ZnO nanorod:
It weighs 0.2g zinc acetate to dissolve in 60mL ethyl alcohol, while weighing 0.15g KOH and being dissolved in 65mL ethyl alcohol, later by two parts
Solution is spare at a temperature of being placed in -10 DEG C (being denoted as A).
It weighs 2g zinc nitrate and 0.5g hexa is dissolved in 400mL distilled water oil bath heating to after 60 DEG C, be added
Temperature is risen to 90 DEG C, whisks Temperature fall after 2h by mixed solution A, and centrifuge washing is drying to obtain ZnO nanorod.
2) preparation of ZnO@silicon dioxide nano rod:
The ZnO nanorod template for weighing 0.1g is uniformly dispersed in 20mLH2O、120mL CH3CH2OH and 20mL NH3•H2O's is mixed
Close in solution, the positive cinnamic acid tetrem vinegar (TEOS) of 60 μ L be added dropwise in the state of whisking later, continues to whisk 1h, with water and
Ethanol washing is drying to obtain ZnO@silicon dioxide nano rod.
3) ZnO@SiO2The preparation of@Graphene nano-rod network:
The ZnO@silicon dioxide nano rod of 0.5g is dispersed in the NaCl aqueous solution that 60mL concentration is 0.5mol/L, is then added dropwise
0.75g diallyl dimethyl ammoniumchloride (PDDA), centrifuge washing three times, disperses 30mL for nanometer rods later after whisking 1h
In distilled water, 30mL graphene oxide dispersion (0.2g) is added dropwise in the state of whisking, continues to whisk 6h, be centrifuged three times, again
It is scattered in distilled water, NaBH is added dropwise4Solution (2gNaBH4It is dissolved in 10mL distilled water), centrifuge washing is dry.
4) SiO2The preparation of@G nanotube network:
It is washed using the HC1 solution of 1mol/L, ZnO template is removed, the SiO of final product graphene coated is obtained2Nanotube
Network.
Embodiment 3
A kind of preparation method of nanometer rods composite negative pole material, hollow core-shell structure is presented in nanometer rods composite negative pole material, interior
Core is silica, and shell is the network structure that graphene is formed；Its detailed preparation process is as follows:
1) preparation of ZnO nanorod:
It weighs 0.4g zinc acetate to dissolve in 60mL ethyl alcohol, while weighing 0.3g KOH and being dissolved in 65mL ethyl alcohol, later by two parts
Solution is spare at a temperature of being placed in 0 DEG C (being denoted as A).
It weighs 3g zinc nitrate and 0.7g hexa is dissolved in 400mL distilled water oil bath heating to after 60 DEG C, be added
Temperature is risen to 90 DEG C, whisks Temperature fall after 2h by mixed solution A, and centrifuge washing is drying to obtain ZnO nanorod.
2) preparation of ZnO@silicon dioxide nano rod:
The ZnO nanorod template for weighing 0.3g is uniformly dispersed in 20mLH2O、120mL CH3CH2OH and 20mL NH3•H2O's is mixed
Close in solution, the positive cinnamic acid tetrem vinegar (TEOS) of 60 μ L be added dropwise in the state of whisking later, continues to whisk 1h, with water and
Ethanol washing is drying to obtain ZnO@silicon dioxide nano rod.
3) ZnO@SiO2The preparation of@Graphene nano-rod network:
The ZnO@silicon dioxide nano rod of 0.5g is dispersed in the NaCl aqueous solution that 60mL concentration is 0.5mol/L, is then added dropwise
0.75g diallyl dimethyl ammoniumchloride (PDDA), centrifuge washing three times, disperses 30mL for nanometer rods later after whisking 1h
In distilled water, 30mL graphene oxide dispersion (0.2g) is added dropwise in the state of whisking, continues to whisk 6h, be centrifuged three times, again
It is scattered in distilled water, NaBH is added dropwise4Solution (2gNaBH4It is dissolved in 10mL distilled water), centrifuge washing is dry.
4) SiO2The preparation of@G nanotube network:
It is washed using the HC1 solution of 1mol/L, ZnO template is removed, the SiO of final product graphene coated is obtained2Nanotube
Network.
Comparative example
After the silica of 0.5g is mixed with 30mL graphene oxide dispersion (0.2g), after mixing evenly, NaBH is added dropwise4It is molten
Liquid (2gNaBH4It is dissolved in 10mL distilled water), centrifuge washing is dry.
The following test of design:
SEM test
Fig. 1 is the SiO for the graphene coated that embodiment 1 is prepared2The SEM picture of nanotube, as can be seen from Figure, material is in
Existing hollow, tubular structure.
Button cell
Lithium ion battery negative material obtained in Examples 1 to 3 and comparative example is assembled into button cell A1, A2, A3 respectively
And B1；Preparation method are as follows: add binder, conductive agent and solvent in negative electrode material, be stirred slurrying, be coated in copper foil
On, it is obtained by drying, rolling.Binder used be LA132 binder, conductive agent SP, negative electrode material be Examples 1 to 3 and
The negative electrode material that comparative example is prepared, solvent are secondary distilled water, its ratio be: negative electrode material: SP:LA132: secondary distilled water
=95g:1g:4g:220mL；Electrolyte is LiPF6/ EC+DEC (1:1), metal lithium sheet are to electrode, and diaphragm uses polyethylene
(PE), polypropylene (PP) or poly- second propylene (PEP) composite membrane, simulated battery are assemblied in the glove box for be flushed with hydrogen gas and carry out, electrification
It learns performance to carry out on the new prestige 5v/10mA type cell tester of the blue electricity in Wuhan, charging/discharging voltage range is 0.005V to 2.0V, is filled
Discharge rate is 0.1C.
Table 1, embodiment and comparative example buckle electrical test results comparison
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example | |
| Discharge capacity (mAh/g) for the first time | 732.7 | 716.7 | 708.5 | 556.8 |
| First charge discharge efficiency (%) | 89.1 | 88.8 | 87.3 | 82.4 |
As can be seen from Table 1, the discharge capacity and its efficiency for the composite negative pole material that embodiment is prepared are apparently higher than comparative example,
Its reason by hydro-thermal reaction can interlayer by silicon materials Uniform Doped in graphene and surface, and it is highly conductive by graphene
Property the characteristics of, the gram volume for improving nano silicon material plays, and simultaneous oxidation graphene and nano silicon material have stronger absorption
Power improves the binding force between its material.
Soft-package battery test
Respectively with embodiment 1, embodiment 2, the material that embodiment 3 and comparative example are prepared is as negative electrode material, with LiFePO4
For positive electrode, using LiPF6/ EC+DEC(volume ratio 1: 1) being electrolyte, and 2400 film of Celgard is diaphragm, prepares 5AH
Soft-package battery C1, C2, C3, D1 and its corresponding cathode pole piece, and it is swollen to test the imbibition liquid-keeping property of its cathode pole piece, battery core
The cycle performance of swollen rate and its soft-package battery；
The imbibition liquid-keeping property contrast table of table 2, different materials
| Rate of liquid aspiration (mL/min) | It protects liquid rate (electrolyte content/0h electrolyte content for 24 hours) | |
| Embodiment 1 | 6.1 | 95.3% |
| Embodiment 2 | 5.6 | 94.2% |
| Embodiment 3 | 4.8 | 94.4% |
| Comparative example | 2.1 | 83.7% |
As can be seen from Table 2, the imbibition liquid-keeping property of embodiment 1-3 material is apparently higher than comparative example, reason may with it is compound
Negative electrode material hydrogen peroxide oxidation forms hole on the surface of graphene, improves its imbibition liquid-keeping property；Novel dried skill is used simultaneously
The nano aperture that art is formed, can be further improved the imbibition liquid-keeping property of material.
The rebound rate contrast table of table 3, pole piece
| Example | Pole piece rebound rate (%) |
| Embodiment 1 | 4.8 |
| Embodiment 2 | 5.6 |
| Embodiment 3 | 5.1 |
| Comparative example | 9.6 |
By table 3, it can be seen that the cathode pole piece rebound rate that embodiment is prepared is significantly lower than the rebound rate of comparative example pole piece,
Reason may be that kernel is hollow structure, so that its silicon-carbon cathode material is provided buffering in charge and discharge process, reduces its expansion rate.
Table 4, different materials circulation compare figure
| Embodiment | Initial capacity (Ah) | Capacity (Ah) after 500 times |
| Embodiment 1 | 5.24 | 4.64 |
| Embodiment 2 | 5.27 | 4.63 |
| Embodiment 3 | 5.26 | 4.54 |
| Comparative example | 5.21 | 4.09 |
| Embodiment | Initial capacity conservation rate (%) | Recycle 500 conservation rates (%) |
| Embodiment 1 | 100 | 88.62 |
| Embodiment 2 | 100 | 87.78 |
| Embodiment 3 | 100 | 86.39 |
| Comparative example | 100 | 78.55 |
As can be seen from Table 4, the cycle performance of embodiment 1-3 is obviously due to comparative example, the reason for this is that in charge and discharge process, silicon-carbon
Volume dilatation is high, and kernel hollow structure provides cushion space for lithium ion in charge and discharge process, reduces its expansion rate and mentions
Its high cycle performance；The graphene of shell is to provide electron channel in charge and discharge process, and further increase its cyclicity simultaneously
Energy.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (1)
1. a kind of preparation method of nanometer rods composite negative pole material, it is characterised in that: nanometer rods composite negative pole material presents hollow
Core-shell structure, kernel is silica, and shell is the network structure that graphene is formed；Its detailed preparation process is as follows:
1) preparation of ZnO nanorod:
It weighs (0.2~0.4) g zinc acetate to dissolve in 60mL ethyl alcohol, while weighing (0.15~0.3) g KOH and being dissolved in 65mL second
In alcohol, two parts of solution are placed in spare (being denoted as A) at a temperature of (- 10~0) DEG C later；
It weighs (2~3) g zinc nitrate and (0.5~0.7) g hexa is dissolved in 400mL distilled water oil bath heating to 60 DEG C
Afterwards, mixed solution A is added, temperature is risen to 90 DEG C, whisks Temperature fall after 2h, centrifuge washing is drying to obtain ZnO nanorod；
2) preparation of ZnO@silicon dioxide nano rod:
The ZnO nanorod template for weighing (0.1~0.3) g is uniformly dispersed in 20mL H2O、120mL CH3CH2OH and 20mL
NH3•H2In the mixed solution of O, the positive cinnamic acid tetrem vinegar (TEOS) of 60 μ L is added dropwise in the state of whisking later, continues to pull
1h is mixed, with water and ethanol washing, is drying to obtain ZnO@silicon dioxide nano rod；
3) ZnO@SiO2The preparation of@Graphene nano-rod network:
The ZnO@silicon dioxide nano rod of 0.5g is dispersed in the NaCl aqueous solution that 60mL concentration is 0.5mol/L, is then added dropwise
0.75g diallyl dimethyl ammoniumchloride (PDDA), centrifuge washing three times, disperses 30mL for nanometer rods later after whisking 1h
In distilled water, 30mL graphene oxide dispersion (0.2g) is added dropwise in the state of whisking, continues to whisk 6h, be centrifuged three times, again
It is scattered in distilled water, NaBH is added dropwise4Solution (2g NaBH4It is dissolved in 10mL distilled water), centrifuge washing is dry；
4) preparation of SiO2@G nanotube network:
It is washed using the HC1 solution of 1mol/L, ZnO template is removed, the SiO2 nanotube of final product graphene coated is obtained
Network.
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| CN110611092B (en) * | 2019-10-11 | 2022-08-02 | 中国石油大学(华东) | Preparation method of nano silicon dioxide/porous carbon lithium ion battery cathode material |
| CN111171383A (en) * | 2020-02-11 | 2020-05-19 | 贵州大学 | Preparation method and application of porous load type rubber vulcanization accelerator |
| CN114574556A (en) * | 2022-02-23 | 2022-06-03 | 宁德师范学院 | Oxygen vacancy titanium dioxide @ graphene-based DNA methylation photoelectric detection method |
| CN114574556B (en) * | 2022-02-23 | 2023-05-30 | 宁德师范学院 | Oxygen vacancy titanium dioxide@graphene-based DNA methylation photoelectric detection method |
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