CN110289403A - A kind of Nano carbon balls and its preparation method and application containing monatomic Fe - Google Patents
A kind of Nano carbon balls and its preparation method and application containing monatomic Fe Download PDFInfo
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- CN110289403A CN110289403A CN201910503538.7A CN201910503538A CN110289403A CN 110289403 A CN110289403 A CN 110289403A CN 201910503538 A CN201910503538 A CN 201910503538A CN 110289403 A CN110289403 A CN 110289403A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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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- H01M10/052—Li-accumulators
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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
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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Abstract
The present invention relates to a kind of Nano carbon balls and its preparation method and application containing monatomic Fe, it carries out polymerization reaction under the action of iron-containing catalyst and oxidant and obtains polypyrrole ball dispersion liquid the following steps are included: pyrroles is added to the water by (a)；(b) by the polypyrrole ball dispersion liquid it is dry the presoma of nanosphere containing Fe；(c) presoma of nanosphere containing Fe is placed in inert atmosphere and carries out calcining carbonization.Having used a kind of simple, method without template to synthesize includes the Nano carbon balls material of the N doping of monatomic Fe, and the presence of monatomic Fe can reduce the nucleation overpotential of Li dendrite, so that Li dendrite is in negative terminal surface homogeneous nucleation, it is suppressed that the growth of Li dendrite；The structure of another aspect Nano carbon balls has also well reconciled volume expansion and the mechanical tension that generates, maintains the electrochemistry integrality of structure.
Description
Technical field
The invention belongs to lithium metal battery fields, and in particular to a kind of iron content Nano carbon balls, and in particular to one kind is containing single former
The Nano carbon balls and its preparation method and application of sub- Fe.
Background technique
Traditional fossil energy is gradually deficient and its baneful influence caused by environment, accelerates people to clean energy resource
With the research of renewable energy.Electric energy causes extensive concern as one kind of clean energy resource, and wherein rechargeable battery is in mistake
It is even more to provide energy safeguard for portable electronic device and electric vehicle in the more than ten years gone.In new energy storage system, lithium gold
Belong to cathode with its high theoretical capacity (3860mA h/g), extremely low chemical potential (- 3.040V vs standard hydrogen electrode) and low
Density (0.534g cm-3), and cause the extensive concern of researcher.
But the practical application of lithium ion battery has also suffered from many obstructions, wherein most important is exactly cyclic process
The growth of middle Li dendrite can destroy solid electrolyte phase interface (SEI) along with huge volume change, expose the gold of the inside
Belong to lithium, then lithium metal and electrolyte reaction, reduce the lithium and electrolyte that can be worked, so as to cause coulombic efficiency and energy
The reduction of density.In addition, also to bring huge safety to battery hidden for the chemical activity and electro-chemical activity of this height of lithium metal
Suffer from.
For inhibiting the growth of Li dendrite, researchers have done a large amount of work: on the one hand, by modification electrolyte or
Person is added film for additive and comes the interface between stable metal lithium and electrolyte；On the other hand, solid electrolyte or people are utilized
For the protective film for doing a physics be also inhibit Li dendrite effective ways.The former compared to liquid electrolyte, do not reveal,
The shortcomings that inflammable, poor chemical stability, and mechanical modulus with higher, can be very good to solve safety issue, still
Ionic conductivity difference limits its commercial applications.The latter can use blade coating, and the method for magnetron sputtering, atomic layer deposition etc. exists
One layer of protective layer for being similar to SEI film is plated on cathode of lithium surface, and directionality is strong, can obtain the boundary layer of certain specific components, but
It is overly dependent upon equipment and treatment process.Lithium metal, which is embedded into graphite layers, effectively to be inhibited in Li dendrite and cyclic process
Volume expansion, obtain the lithium ion battery of higher-security and realize commercial applications, therefore the present invention devises one
For Nano carbon balls of the kind containing monatomic Fe as skeleton, equally distributed monatomic Fe can reduce the nucleation overpotential of Li dendrite,
Make Li dendrite homogeneous nucleation, to effectively inhibit the growth and volume expansion of Li dendrite, is obtained with the button cell that this is assembled
Obtained good chemical property.
Summary of the invention
A kind of system of Nano carbon balls containing monatomic Fe is provided the invention aims to overcome the deficiencies in the prior art
Preparation Method.
In order to achieve the above objectives, the technical solution adopted by the present invention is that: a kind of preparation of the Nano carbon balls containing monatomic Fe
Method, it the following steps are included:
(a) pyrroles is added to the water, polymerization reaction is carried out under the action of iron-containing catalyst and oxidant and obtains polypyrrole
Ball dispersion liquid；The pyrroles, iron-containing catalyst, oxidant and water ratio be 1~3ml:0.1~0.4g:8~12ml:70~
110ml；
(b) by the polypyrrole ball dispersion liquid it is dry the presoma of nanosphere containing Fe；
(c) presoma of nanosphere containing Fe is placed in inert atmosphere and carries out calcining carbonization.
Optimally, in step (a), the iron-containing catalyst is FeCl2·4H2O。
Further, in step (a), the oxidant is the hydrogen peroxide solution that mass concentration is 20~35%.
Further, in step (a), after iron-containing catalyst mixing is first added, dripping hydrogen peroxide solution is in 10~30
It DEG C is stirred to react 4~8 hours.
Optimally, in step (c), the inert gas is argon gas, and volume flow is 100~300sccm；Calcination temperature
For 600~1000 DEG C and calcination time is 2~5h.
Another object of the present invention is to provide a kind of Nano carbon balls containing monatomic Fe, it is by any of the above-described described containing single
The preparation method of the Nano carbon balls of atom Fe is made.
A further object of the present invention is to provide a kind of applications of above-mentioned Nano carbon balls containing monatomic Fe, are contained described
The Nano carbon balls of monatomic Fe are used for lithium metal battery as negative electrode active material.
Due to the above technical solutions, the present invention has the following advantages over the prior art: the present invention is containing monatomic
The preparation method of the Nano carbon balls of Fe, having used a kind of simple, method without template to synthesize includes that the nitrogen of monatomic Fe is mixed
Miscellaneous Nano carbon balls material (abbreviation FeSA- N-C), the presence of monatomic Fe can reduce the nucleation overpotential of Li dendrite, so that lithium
Dendrite is in negative terminal surface homogeneous nucleation, it is suppressed that the growth of Li dendrite；The structure of another aspect Nano carbon balls also well reconciles
Volume expansion and the mechanical tension generated, maintain the electrochemistry integrality of structure.Therefore, this electrode material is shown very
High coulombic efficiency, cyclical stability are also good.It is worth noting that, the invention material price is cheap, production method is simply easy
Row, can carry out large scale preparation.
Detailed description of the invention
Fig. 1 is the energy disperse spectroscopy elemental analysis figure and the angle of elevation of the Nano carbon balls containing monatomic Fe prepared by the embodiment of the present invention 1
Spend annular dark field scanning transmission electron microscope figure: (a) energy disperse spectroscopy elemental analysis figure and relevant (b) carbon, (c) nitrogen member
The figure of element, (d) Fe elemental map, (e) high angle annular dark field scanning transmission electron microscope figure and (f) amplification a portion；
Fig. 2 is the scanning electron microscope (SEM) photograph of the Nano carbon balls containing monatomic Fe prepared by the embodiment of the present invention 1；
Fig. 3 is Fe prepared by the embodiment of the present invention 1SA- N-C is used for the coulombic efficiency figure of lithium metal battery cathode protection；
Fig. 4 is Fe prepared by the embodiment of the present invention 2SA- N-C is used for the full battery stable circulation of lithium metal battery cathode protection
Property figure.
Specific embodiment
The preparation method of Nano carbon balls of the present invention containing monatomic Fe, it is the following steps are included: water is added in pyrroles by (a)
In, polymerization reaction, which is carried out, under the action of iron-containing catalyst and oxidant obtains polypyrrole ball dispersion liquid；The pyrroles, iron content are urged
The ratio of agent, oxidant and water is preferably 1~3ml:0.1~0.4g:8~12ml:70~110ml；(b) by the polypyrrole
Ball dispersion liquid it is dry the presoma of nanosphere containing Fe；(c) presoma of nanosphere containing Fe is placed in inert atmosphere and is forged
Burn carbonization.Synthesized present invention uses a kind of simple, method without template include monatomic Fe N doping carbon
Nanometer ball material (abbreviation FeSA-N-C；It will be dissolved if it is simple substance Fe or other nanoclusters, can't detect Fe's
Signal, but still can detecte the signal of Fe with synchrotron radiation test after this sample treatment, and be determined as monatomic
Fe), the presence of monatomic Fe can reduce the nucleation overpotential of Li dendrite, so that Li dendrite is in negative terminal surface homogeneous nucleation, suppression
The growth of Li dendrite is made；The structure of another aspect Nano carbon balls has also well reconciled volume expansion and the machinery that generates
Power maintains the electrochemistry integrality of structure.Therefore, this electrode material shows very high coulombic efficiency, cyclical stability
Also good.It is worth noting that, the invention material price is cheap, production method is simple and easy, can carry out large scale preparation.
In step (a), the iron-containing catalyst is usually FeCl2·4H2O；The oxidant is that mass concentration is usually 20
~35% hydrogen peroxide solution.In step (a), after iron-containing catalyst mixing is first added, dripping hydrogen peroxide solution is in 10~30
It DEG C is stirred to react 4~8 hours.In step (c), the inert gas is argon gas, and volume flow is 100~300sccm；Calcining
Temperature is 600~1000 DEG C and calcination time is 2~5h.
The present invention also provides a kind of Nano carbon balls applications obtained above containing monatomic Fe, it is as negative electrode active material
For lithium metal battery.Specifically: using lithium piece as cathode, Tu Liao FeSAThe copper foil of-N-C is anode, bis- (fluoroforms containing 1mol/L
Alkane sulphonyl) imine lithium (LiTFSI) is dissolved in 1,3- dioxolanes (DOL), 1,2- dimethoxy-ethane (DME) 1:1 in mass ratio is mixed
The electrolyte formed is closed as electrolyte, Celgard 2400 is fabricated to button cell (CR2025) as diaphragm.On copper foil
FeSAThe amount of-N-C is 1~3mg, and the amount of conductive agent acetylene black is 0.1~0.3mg, and the amount of binder Kynoar (pvdf) is
0.1~0.3mg, the dosage of electrolyte are 30~45 μ L.Also lithium is deposited on and has applied FeSAFollowing group is used as on the copper foil of-N-C
Cathode in the full battery of dress.Full battery LiCoO2As anode, the LiPF of 1mol/L6(lithium hexafluoro phosphate) is dissolved in carbonic acid second
Electrolyte, Celgard 2400 are used as in enester (EC), diethyl carbonate (DEC) electrolyte that 1:1 is mixed to form by volume
Button cell (CR2025), which is fabricated to, as diaphragm surveys cyclical stability.The capacity of lithium deposition is 1~5mAh/cm2.In aluminium foil
It is upper to apply the LiCoO mixed in proportion2, acetylene black and polytetrafluoroethylene (PTFE) (pvdf) as anode, wherein LiCoO2Amount be 1~
The amount of 3mg, conductive agent acetylene black and polyfluortetraethylene of binding element (pvdf) is 0.1~0.3mg.
Below in conjunction with example, invention is further explained.
Embodiment 1
The present embodiment provides a kind of preparation method and applications of Nano carbon balls containing monatomic Fe, comprising the following steps:
(a) under room temperature environment, 50mLH is added into beaker2O, 2mL pyrroles is uniformly mixed；Add 40ml H2O、
0.2g FeCl2·4H2O is uniformly mixed, 10mL H is slowly added dropwise2O2(mass concentration 20%), the rapid blackening of solution (10~
30 DEG C), stirring 6h obtains polypyrrole ball dispersion liquid；
(b) polypyrrole ball dispersion liquid is freeze-dried to obtain the presoma of nanosphere containing Fe；
(c) Fe nanosphere presoma will be contained to be placed in tube furnace, in 900 DEG C of calcining 2h in argon atmosphere (200sccm)
Obtain Nano carbon balls (the i.e. Fe containing monatomic FeSA- N-C nanometers of ball materials)；Its energy disperse spectroscopy elemental analysis figure high angle annular is dark
Field scan transmission electron microscope figure is as shown in Figure 1, scanning electron microscope (SEM) photograph is as shown in Figure 2.
By above-mentioned FeSA- N-C nanometers of ball materials are specific as follows for making button cell and full battery:
(1) using lithium piece as cathode, Tu Liao FeSAThe copper foil of-N-C is anode, bis- (fluoroform sulphonyl) imines containing 1mol/L
The electricity that lithium (LiTFSI) is dissolved in 1,3- dioxolanes (DOL), 1,2- dimethoxy-ethane (DME) 1:1 in mass ratio is mixed to form
Liquid is solved as electrolyte, Celgard 2400 is fabricated to button cell (CR2025) as diaphragm.Fe on copper foilSAThe amount of-N-C
For 2mg, the amount of conductive agent acetylene black is 0.25mg, and the amount of binder Kynoar (pvdf) is 0.2mg.The dosage of electrolyte
For 40 μ L.FeSAThe coulombic efficiency figure of-N-C for the protection of lithium metal battery cathode is as shown in Figure 4.
(2) with LiCoO2As anode, the LiPF of 1mol/L6It is dissolved in ethylene carbonate (EC), diethyl carbonate (DEC) is pressed
Electrolyte is used as in the electrolyte that volume ratio 1:1 is mixed to form, Celgard 2400 is fabricated to button cell as diaphragm
(CR2025) cyclical stability is surveyed.The capacity of lithium deposition is 2mAh/cm2.The LiCoO mixed in proportion is applied on aluminium foil2, acetylene
Black and polytetrafluoroethylene (PTFE) (pvdf) is used as anode, wherein LiCoO2Amount be 1.5mg, the amount of conductive agent acetylene black is 0.2mg, is glued
The amount for tying agent Kynoar (pvdf) is 0.3mg, and the dosage of electrolyte is that 32 μ L survey cycle performance.
Embodiment 2
The present embodiment provides a kind of preparation method and applications of Nano carbon balls containing monatomic Fe, in it and embodiment 1
It is almost the same, unlike: in step (a), pyrroles and FeCl2·4H2The usage amount of O is respectively 3ml, 0.4g.
Embodiment 3
The present embodiment provides a kind of preparation method and applications of Nano carbon balls containing monatomic Fe, in it and embodiment 1
It is almost the same, unlike: in step (a), pyrroles and FeCl2·4H2The usage amount of O is respectively 1ml, 0.1g.
Embodiment 4
The present embodiment provides a kind of preparation method and applications of Nano carbon balls containing monatomic Fe, in it and embodiment 1
It is almost the same, unlike: in step (c), calcination temperature is 600 DEG C, calcination time 5h.
Comparative example 1
The present embodiment provides a kind of preparation method and applications of Nano carbon balls, it with it is almost the same in embodiment 1, no
With: in step (a), FeCl2·4H2The usage amount of O is excessive, is 1g.
Comparative example 2
The present embodiment provides a kind of preparation method and applications of Nano carbon balls, it with it is almost the same in embodiment 1, no
With: in step (a), FeCl is not used2·4H2O。
The battery performance table of nanosphere in 1 embodiment 1-5 of table, comparative example 1-2
The foregoing examples are merely illustrative of the technical concept and features of the invention, its object is to allow person skilled in the art
It cans understand the content of the present invention and implement it accordingly, it is not intended to limit the scope of the present invention.It is all smart according to the present invention
Equivalent change or modification made by refreshing essence, should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of preparation method of the Nano carbon balls containing monatomic Fe, which is characterized in that it the following steps are included:
(a) pyrroles is added to the water, polymerization reaction is carried out under the action of iron-containing catalyst and oxidant and obtains polypyrrole ball point
Dispersion liquid；In step (a), the pyrroles, iron-containing catalyst, oxidant and water ratio be g:8 ~ 12 1 ~ 3 ml:0.1 ~ 0.4
The ml of ml:70 ~ 110；
(b) by the polypyrrole ball dispersion liquid it is dry the presoma of nanosphere containing Fe；
(c) presoma of nanosphere containing Fe is placed in inert atmosphere and carries out calcining carbonization.
2. the preparation method of the Nano carbon balls according to claim 1 containing monatomic Fe, it is characterised in that: in step (a), institute
Stating iron-containing catalyst is FeCl2·4H2O。
3. the preparation method of the Nano carbon balls according to claim 2 containing monatomic Fe, it is characterised in that: in step (a), institute
Stating oxidant is the hydrogen peroxide solution that mass concentration is 20 ~ 35%.
4. the preparation method of the Nano carbon balls according to claim 3 containing monatomic Fe, it is characterised in that: in step (a), first
After iron-containing catalyst mixing is added, dripping hydrogen peroxide solution is stirred to react 4 ~ 8 hours in 10 ~ 30 DEG C.
5. the preparation method of the Nano carbon balls according to claim 1 containing monatomic Fe, it is characterised in that: in step (c), institute
Stating inert gas is argon gas, and volume flow is 100 ~ 300 sccm；Calcination temperature is 600 ~ 1000 DEG C and calcination time is 2 ~ 5
h。
6. a kind of Nano carbon balls containing monatomic Fe, it is by the Nano carbon balls containing monatomic Fe any in claim 1 to 6
Preparation method be made.
7. the application of the Nano carbon balls containing monatomic Fe described in claim 6, it is characterised in that: the carbon containing monatomic Fe is received
Rice ball is used for lithium metal battery as negative electrode active material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112058301A (en) * | 2020-10-13 | 2020-12-11 | 北京理工大学 | Preparation method of pyrrole-derived monoatomic iron-based nitrogen-carbon material for oxygen reduction |
| CN113410479A (en) * | 2021-06-17 | 2021-09-17 | 济南大学 | Preparation method and application of transition metal monoatomic and nitrogen-phosphorus-doped carbon sphere |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863617A (en) * | 2011-07-04 | 2013-01-09 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of polypyrrole nanometer microspheres |
| CN104558602A (en) * | 2015-01-27 | 2015-04-29 | 齐鲁工业大学 | Method for preparing polypyrrole micron/nano hollow spheres by adopting one step process |
| CN105024053A (en) * | 2015-06-19 | 2015-11-04 | 苏州大学 | Preparation method for carbon nanometer net containing Fe/Fe3C, carbon nanometer net prepared by using same and application of carbon nanometer net |
| CN107556475A (en) * | 2017-09-12 | 2018-01-09 | 太原理工大学 | The synthetic method of the controllable spherical polypyrrole of size |
-
2019
- 2019-06-12 CN CN201910503538.7A patent/CN110289403A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863617A (en) * | 2011-07-04 | 2013-01-09 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of polypyrrole nanometer microspheres |
| CN104558602A (en) * | 2015-01-27 | 2015-04-29 | 齐鲁工业大学 | Method for preparing polypyrrole micron/nano hollow spheres by adopting one step process |
| CN105024053A (en) * | 2015-06-19 | 2015-11-04 | 苏州大学 | Preparation method for carbon nanometer net containing Fe/Fe3C, carbon nanometer net prepared by using same and application of carbon nanometer net |
| CN107556475A (en) * | 2017-09-12 | 2018-01-09 | 太原理工大学 | The synthetic method of the controllable spherical polypyrrole of size |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112058301A (en) * | 2020-10-13 | 2020-12-11 | 北京理工大学 | Preparation method of pyrrole-derived monoatomic iron-based nitrogen-carbon material for oxygen reduction |
| CN113410479A (en) * | 2021-06-17 | 2021-09-17 | 济南大学 | Preparation method and application of transition metal monoatomic and nitrogen-phosphorus-doped carbon sphere |
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