CN106315665B - A kind of GeO for preparing high charge-discharge capacity2The method of sub-micrometer rod - Google Patents
A kind of GeO for preparing high charge-discharge capacity2The method of sub-micrometer rod Download PDFInfo
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- CN106315665B CN106315665B CN201610650177.5A CN201610650177A CN106315665B CN 106315665 B CN106315665 B CN 106315665B CN 201610650177 A CN201610650177 A CN 201610650177A CN 106315665 B CN106315665 B CN 106315665B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G17/00—Compounds of germanium
- C01G17/02—Germanium dioxide
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
A kind of GeO for preparing high charge-discharge capacity2The method of sub-micrometer rod, is related to technical field of lithium ion battery negative, first by Ca (NO3)2The aqueous solution and GeO2Ammonia spirit mixed, obtain mixed liquor；Above-mentioned mixed liquor is added in hydrothermal reaction kettle, 5 ~ 20 h are reacted at 160 ~ 220 DEG C, germanic acid calcium sub-micrometer rod is obtained；Then obtained germanic acid calcium sub-micrometer rod powder is added in concentrated nitric acid and performed etching, etch period is 0.5 ~ 3 h；The sediment after etching is centrifuged out, and sediment is calcined 1 ~ 3 hour in Muffle furnace at 500 ~ 600 DEG C, described GeO is produced2Sub-micrometer rod.GeO prepared by the present invention2Sub-micrometer rod can be used as lithium ion battery negative material, and it shows higher charge/discharge capacity, and with good cycle performance.
Description
Technical field
The invention belongs to inorganic energy storage material technical field, it is related to lithium ion battery negative material, and in particular to one kind system
The GeO of standby high charge-discharge capacity2The method of sub-micrometer rod.
Background technology
In recent years, with continuous worsening and fossil fuel the shortage of environment, few and zero-emission the hybrid power of blowdown
Automobile and pure electric automobile obtain wideling popularize for national governments, as the new-energy automobile first developed.And new-energy automobile
Key position be power supply, current optimal power supply is lithium ion battery, because it has energy density high, power is close
Degree is high, and operating voltage is high, has extended cycle life, environmental pollution is small, the advantages of self discharge is small.To meet people's life requirement, new energy
The performance of source automobile, especially once charge stroke, it is necessary to further improves.This just proposes higher to lithium ion battery
It is required that.
Electrode is the core component of lithium ion battery, and electrode material decides the capacity of battery.The raising palpus of battery capacity
Start with from electrode material.At present, the graphite cathode material used in lithium ion battery, theoretical capacity only has 372 mAh/g, Er Qiecun
In certain safety issue.And the GeO of stable chemical performance2Negative material has relatively low operating voltage（0 ~ 0.4 V）,
Higher theoretical capacity（1100 mAh/g）, it is adapted to substitute graphite.At present, relevant GeO2The research of negative material is in full generation
Gradually rise on boundary.
Although GeO2With lot of advantages, but its disadvantage existed is that Volume Changes are acute in charge and discharge process
It is strong, so as to influence the cycle performance of material.It is main at present to use and conductive material for this problem, such as agraphitic carbon, graphite
The compound method such as alkene, CNT buffers GeO2Volume Changes, and then improve its cycle performance.
The content of the invention
There is high charge-discharge capacity, and the GeO of good cycle it is an object of the invention to provide one kind2Lithium ion battery
Negative material, with and preparation method thereof.
To achieve the above object, technical scheme of the invention is as follows：A kind of GeO for preparing high charge-discharge capacity2Sub-micro
The method of rice rod, step is as follows：
（1）, by Ca (NO3)2The aqueous solution and GeO2Ammonia spirit mixed, obtain mixed liquor；
（2）, above-mentioned mixed liquor is added in hydrothermal reaction kettle, 5 ~ 20 h are reacted at 160 ~ 220 DEG C, germanic acid is obtained
Calcium sub-micrometer rod；
（3）, obtained germanic acid calcium sub-micrometer rod powder be added in concentrated nitric acid performed etching, etch period is 0.5 ~
3 h；
（4）, centrifuge out the sediment after etching, and by sediment in Muffle furnace calcining 1 at 500 ~ 600 DEG C ~
3 hours, produce described GeO2Sub-micrometer rod.
Further, step（1）In, Ca (NO3)2The aqueous solution and GeO2Ammonia spirit in mixing, Ca and Ge's rubs
You are than being 1.1 ~ 1.2：1.
Step（3）In, the mass ratio of concentrated nitric acid and germanic acid calcium sub-micrometer rod powder is more than 10：1.
Beneficial effect：
The present invention using germanic acid calcium sub-micrometer rod as template is sacrificed, using concentrated nitric acid as template etching agent, using sacrificial
Domestic animal template is finally prepared for GeO2Sub-micrometer rod.Wherein, using the highly acid of concentrated nitric acid, dissolve in germanic acid calcium sub-micrometer rod
Ca compositions, and its strong oxidizing property can preserve GeO2Composition, due to pattern memory effect, the GeO of final gained2Still retain
Sub-micrometer rod pattern.
GeO prepared by the present invention2Sub-micrometer rod, the nm of diameter 200 ~ 500,2 ~ 10 μm of length, can as lithium from
Sub- cell negative electrode material is used, under 100 mA/g current density, GeO2The reversible capacity first of sub-micrometer rod electrode（I.e.
Charging capacity）For 1050 ~ 1080 mAh/g, by 100 circulations, capability retention is 80% ~ 85%, its show compared with
High charge/discharge capacity, and with good cycle performance.
Brief description of the drawings
Fig. 1 is the XRD of the germanium dioxide sub-micrometer rod of the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope diagram of the germanium dioxide sub-micrometer rod of the embodiment of the present invention 1.
Fig. 3 is that discharge and recharge of the germanium dioxide sub-micrometer rod of the embodiment of the present invention 1 under 100 mA/g current density is bent
Line.
Embodiment
Embodiment 1
A kind of GeO for preparing high charge-discharge capacity2The method of sub-micrometer rod, step is as follows：
1）, by Ca (NO3)2Deionized water is dissolved in, the mL of 0.05 M solution 40 is formed；By GeO2Powder adds 10 mL's
In 0.1 M ammonia spirits, it is completely dissolved；Make Ca (NO3)2Solution and GeO2In solution, Ca and Ge mol ratio are 1.1：1, by two
Person's solution is mixed, the min of magnetic agitation 10；
2）, obtained mixed liquor is transferred in 100 mL hydrothermal reaction kettles, add deionized water to reactor cumulative volume
80%, react 5 h at 160 DEG C, obtain germanic acid calcium sub-micrometer rod；
3）, obtained germanic acid calcium sub-micrometer rod powder be added in 10 mL concentrated nitric acid performed etching, etch period is
0.5 h, wherein, the mass ratio of concentrated nitric acid and germanic acid calcium sub-micrometer rod powder is 11：1；
4）, the sediment after etching centrifuged, washed without deionized water or ethanol, the sediment isolated is direct
Calcined 1 hour at 500 DEG C in Muffle furnace, that is, obtain the GeO2Sub-micrometer rod.
As shown in figure 1, X-ray powder diffraction shows, obtained GeO2Sub-micrometer rod is the germanium dioxide of hexagonal phase, right
JCPDS cards are answered to number（36-1463）, free from admixture peak occur, illustrate that product purity is higher.
As shown in Fig. 2 scanning electron microscope (SEM) photograph shows GeO2A diameter of 200 ~ 400 nm of sub-micrometer rod, length is 2 ~ 8 μm.
Germanium dioxide sub-micrometer rod prepared by the present embodiment is used as lithium ion battery negative material, its electrochemistry is tested
Performance.Specific method is as follows：By germanium dioxide sub-micron and conductive agent（Acetylene black）And bonding agent（PVDF）According to mass ratio
80：10：10 ratio uniform mixing.Carefully ground 20 minutes in agate mortar, 1-METHYLPYRROLIDONE solution is added
Into ground mixture, stir until then slurry is equably coated with by mixture in uniform sticky paste
On a diameter of 14 mm copper sheet, copper sheet is put into air dry oven 80 DEG C of dryings 10 hours, that is, electrode to be measured is made.With
Metal lithium sheet is to electrode（Reference electrode）, U.S. production cell guard 2400 are barrier film, 1 M LiPF4EC/DMC solution
For electrolyte, 2032 type button cells are assembled into vacuum glove box.Filled using the LandBT2013A types of the blue electricity production in Wuhan
Discharge instrument carries out charge-discharge performance test to battery.As shown in figure 3, under 100 mA/g current density, the present embodiment is made
The charging and discharging curve of standby germanium dioxide nanometer rods respectively 1, after 10,30,100 circulations.Fig. 3 is shown, 100 mA/g's
Under current density, the germanium dioxide nanometer rods initial charge prepared by the present embodiment（It is i.e. reversible）Capacity is 1065 mAh/g, far
Higher than the capacity of current commercial graphite cathode material（The mAh/g of theoretical value 372）.Through 100 times circulate after, the material it is reversible
Charging capacity still may be up to 853 mAh/g, and capability retention is 80 %.
Embodiment 2
A kind of GeO for preparing high charge-discharge capacity2The method of sub-micrometer rod, step is as follows：
1）, by Ca (NO3)2Deionized water is dissolved in, the mL of 0.15 M solution 40 is formed；By GeO2Powder adds the 0.2 of 6 mL
In M ammonia spirits, it is completely dissolved；Make Ca (NO3)2Solution and GeO2In solution, Ca and Ge mol ratio are 1.1：1, both are molten
Liquid is mixed, the min of magnetic agitation 10；
2）, obtained mixed liquor is transferred in 100 mL hydrothermal reaction kettles, add deionized water to reactor cumulative volume
80%, react 8 h at 170 DEG C, obtain germanic acid calcium sub-micrometer rod；
3）, obtained germanic acid calcium sub-micrometer rod powder be added in 12 mL concentrated nitric acid performed etching, etch period is
1 h, wherein, the mass ratio of concentrated nitric acid and germanic acid calcium sub-micrometer rod powder is 12：1；
4）, the sediment after etching centrifuged, washed without deionized water or ethanol, the sediment isolated is direct
Calcined 2 hours at 500 DEG C in Muffle furnace, that is, obtain the GeO2Sub-micrometer rod.
Germanium dioxide sub-micrometer rod prepared by the present embodiment is used as lithium ion battery negative material, its electrochemistry is tested
Performance.Specific method be the same as Example 1.Charge and discharge is carried out to battery using the LandBT2013A type discharge and recharge instrument of the blue electricity production in Wuhan
Electric performance test.Under 100 mA/g current density, the germanium dioxide nanometer rods initial charge prepared by the present embodiment（
It is inverse）Capacity is 1050 mAh/g.After being circulated through 100 times, the reversible charging capacity of the material still may be up to 861 mAh/g, capacity
Conservation rate is 82 %.
Embodiment 3
A kind of GeO for preparing high charge-discharge capacity2The method of sub-micrometer rod, step is as follows：
1）, by Ca (NO3)2Deionized water is dissolved in, the mL of 0.4 M solution 40 is formed；By GeO2Powder adds the 0.5 of 5 mL
In M ammonia spirits, it is completely dissolved；Make Ca (NO3)2Solution and GeO2In solution, Ca and Ge mol ratio are 1.15：1, it incite somebody to action both
Solution is mixed, the min of magnetic agitation 10；
2）, obtained mixed liquor is transferred in 100 mL hydrothermal reaction kettles, add deionized water to reactor cumulative volume
80%, react 10 h at 180 DEG C, obtain germanic acid calcium sub-micrometer rod；
3）, obtained germanic acid calcium sub-micrometer rod powder be added in 15 mL concentrated nitric acid performed etching, etch period is
3 h, wherein, the mass ratio of concentrated nitric acid and germanic acid calcium sub-micrometer rod powder is 13：1；
4）, the sediment after etching centrifuged, washed without deionized water or ethanol, the sediment isolated is direct
Calcined 1.5 hours at 550 DEG C in Muffle furnace, that is, obtain the GeO2Sub-micrometer rod.
Germanium dioxide sub-micrometer rod prepared by the present embodiment is used as lithium ion battery negative material, its electrochemistry is tested
Performance.Specific method be the same as Example 1.Charge and discharge is carried out to battery using the LandBT2013A type discharge and recharge instrument of the blue electricity production in Wuhan
Electric performance test.Under 100 mA/g current density, the germanium dioxide nanometer rods initial charge prepared by the present embodiment（
It is inverse）Capacity is 1078 mAh/g.After being circulated through 100 times, the reversible charging capacity of the material still may be up to 891 mAh/g, capacity
Conservation rate is 83 %.
Embodiment 4
A kind of GeO for preparing high charge-discharge capacity2The method of sub-micrometer rod, step is as follows：
1）, by Ca (NO3)2Deionized water is dissolved in, the mL of 0.6 M solution 40 is formed；By GeO2Powder adds the 0.7 of 6 mL
In M ammonia spirits, it is completely dissolved；Make Ca (NO3)2Solution and GeO2In solution, Ca and Ge mol ratio are 1.1：1, both are molten
Liquid is mixed, the min of magnetic agitation 10；
2）, obtained mixed liquor is transferred in 100 mL hydrothermal reaction kettles, add deionized water to reactor cumulative volume
80%, react 20 h at 190 DEG C, obtain germanic acid calcium sub-micrometer rod；
3）, obtained germanic acid calcium sub-micrometer rod powder be added in 18 mL concentrated nitric acid performed etching, etch period is
2h, wherein, the mass ratio of concentrated nitric acid and germanic acid calcium sub-micrometer rod powder is 14：1；
4）, the sediment after etching centrifuged, washed without deionized water or ethanol, the sediment isolated is direct
Calcined 2 hours at 600 DEG C in Muffle furnace, that is, obtain the GeO2Sub-micrometer rod.
Germanium dioxide sub-micrometer rod prepared by the present embodiment is used as lithium ion battery negative material, its electrochemistry is tested
Performance.Specific method be the same as Example 1.Charge and discharge is carried out to battery using the LandBT2013A type discharge and recharge instrument of the blue electricity production in Wuhan
Electric performance test.Under 100 mA/g current density, the germanium dioxide nanometer rods initial charge prepared by the present embodiment（
It is inverse）Capacity is 1075 mAh/g.After being circulated through 100 times, the reversible charging capacity of the material still may be up to 903 mAh/g, capacity
Conservation rate is 84 %.
Embodiment 5
A kind of GeO for preparing high charge-discharge capacity2The method of sub-micrometer rod, step is as follows：
1）, by Ca (NO3)2Deionized water is dissolved in, the mL of 1 M solution 40 is formed；By GeO2Powder adds 8 mL 0.9 M
In ammonia spirit, it is completely dissolved；Make Ca (NO3)2Solution and GeO2In solution, Ca and Ge mol ratio are 1.2：1, both are molten
Liquid is mixed, the min of magnetic agitation 10；
2）, obtained mixed liquor is transferred in 100 mL hydrothermal reaction kettles, add deionized water to reactor cumulative volume
80%, react 7 h at 220 DEG C, obtain germanic acid calcium sub-micrometer rod；
3）, obtained germanic acid calcium sub-micrometer rod powder be added in 20 mL concentrated nitric acid performed etching, etch period is
1h, wherein, the mass ratio of concentrated nitric acid and germanic acid calcium sub-micrometer rod powder is 15：1；
4）, the sediment after etching centrifuged, washed without deionized water or ethanol, the sediment isolated is direct
Calcined 3 hours at 500 DEG C in Muffle furnace, that is, obtain the GeO2Sub-micrometer rod.
Germanium dioxide sub-micrometer rod prepared by the present embodiment is used as lithium ion battery negative material, its electrochemistry is tested
Performance.Specific method be the same as Example 1.Charge and discharge is carried out to battery using the LandBT2013A type discharge and recharge instrument of the blue electricity production in Wuhan
Electric performance test.Under 100 mA/g current density, the germanium dioxide nanometer rods initial charge prepared by the present embodiment（
It is inverse）Capacity is 1080 mAh/g.After being circulated through 100 times, the reversible charging capacity of the material still may be up to 920 mAh/g, capacity
Conservation rate is 85 %.
Claims (1)
1. a kind of GeO for preparing high charge-discharge capacity2The method of sub-micrometer rod, it is characterised in that：Step is as follows：
（1）, by Ca (NO3)2The aqueous solution and GeO2Ammonia spirit mixed, obtain mixed liquor；Wherein, Ca and Ge rubs
You are than being 1.1 ~ 1.2：1；
（2）, above-mentioned mixed liquor is added in hydrothermal reaction kettle, 5 ~ 20 h are reacted at 160 ~ 220 DEG C, germanic acid calcium are obtained sub-
Micron bar；
（3）, obtained germanic acid calcium sub-micrometer rod powder be added in concentrated nitric acid performed etching, etch period is 0.5 ~ 3 h；
Wherein, the mass ratio of concentrated nitric acid and germanic acid calcium sub-micrometer rod powder is more than 10：1；
（4）, centrifuge out the sediment after etching, and calcining 1 ~ 3 is small at 500 ~ 600 DEG C in Muffle furnace by sediment
When, produce described GeO2Sub-micrometer rod.
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| CN109248677B (en) * | 2018-06-06 | 2021-06-04 | 青岛农业大学 | Germanium dioxide nanoenzyme and pesticide detection application thereof |
| CN109037652B (en) * | 2018-08-16 | 2021-04-27 | 福州大学 | Preparation method and application of nitrogen-doped carbon-coated graded germanium structure |
| CN110790304A (en) * | 2019-11-13 | 2020-02-14 | 福州大学 | Preparation of germanium dioxide/nitrogen-doped carbon composite material with sea urchin-shaped structure and application of composite material in lithium ion battery |
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| CN102534268A (en) * | 2010-12-28 | 2012-07-04 | 北京有色金属研究总院 | Production method of high-purity germanium dioxide |
| CN102774877B (en) * | 2012-08-03 | 2014-05-14 | 云南驰宏锌锗股份有限公司 | Novel process for preparing germanium dioxide (GeO2) |
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