CN108550815A - A kind of preparation method for the carbon coating silicon substrate composite negative pole material that lithium ion battery nitrogen-doped graphene supports - Google Patents
A kind of preparation method for the carbon coating silicon substrate composite negative pole material that lithium ion battery nitrogen-doped graphene supports Download PDFInfo
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Abstract
The invention belongs to electrochemical material and new energy field, a kind of lithium ion battery negative material and preparation method thereof is disclosed.Preparation method includes the following steps：(1) water-soluble nitrogenous supermolecule column [5] aromatic hydrocarbons is introduced into graphene oxide solution, obtains the graphene oxide mixed solution of supermolecule modification；(2) nano silica fume is introduced into above-mentioned mixed solution, the silicon materials of graphene support is then obtained by liquid phase reduction；(3) carbon coating is carried out to the product of step (2), obtains the carbon coating silicon substrate composite negative pole material of nitrogen-doped graphene support.There is the negative material of the present invention high electrochemical lithium storage content, excellent cycle performance to have potential application prospect in high performance lithium ion battery field.
Description
Technical field
The invention belongs to electrochemical materials and new energy field, and in particular to a kind of lithium ion battery nitrogen-doped graphene
The preparation method of the carbon coating silicon substrate composite negative pole material of support.
Background technology
According in April, 2017 publication《Automobile industry Long-and Medium-term Development is planned》, arrive the year two thousand twenty, lithium-ion-power cell energy
Metric density need to reach 300Wh/kg or more；By 2025, energy density need to reach 350Wh/kg or more.It uses currently on the market
High voltage stratiform transition metal oxide and the liquid lithium ion power battery that is formed as positive and negative anodes active material of graphite
Energy density generally in 240Wh/kg hereinafter, graphite cathode capacity very close theoretical capacity, room for promotion are limited.To reach
To the energy density in planning, it is most important to develop novel high-capacity negative material.Silicon materials are because with the high embedding lithium of theory
Capacity (4200mAh/g) is far above other negative materials.But due to its huge bulk effect (>300%), silicon electrode material
Understand dusting in charge and discharge process and peeled off from collector so that active material and active material, active material and collector
Between lose electrical contact, while constantly forming new solid-phase electrolyte layer, eventually lead to the deterioration of chemical property.In addition, silicon
It is semi-conducting material, electron conduction is poor, therefore seriously hinders functionization of the silicon as lithium ion battery negative material.
Graphene is a kind of monatomic flat film being made of carbon atom, has excellent physicochemical characteristics, compares table
Area is up to 2620m2/ g, electron mobility is up to 2 × 105cm2V/s, 140 times of electron mobility about in silicon, conductivity can
It is conductive best material at room temperature up to 108 Ω/m.The composite material of silicon and graphene is prepared as negative electrode of lithium ion battery material
Material has many advantages.First, graphene has larger specific surface area, can shorten the transmission range of lithium ion.Secondly, stone
The volumetric stress that silicon materials generate during lithium ion intercalation/deintercalation can be effectively relieved in black alkene.The addition of graphene, may be used also
To increase electrode conductivuty so as to improve chemical properties such as the cycle performance of battery, specific capacity and efficiency for charge-discharges.Recently, miscellaneous
Atom doped graphene is increasingly paid close attention to by researcher such as sulphur, nitrogen and boron doping graphene.With nitrogen-doped graphene
For, after nitrogen doped, the electron conduction of graphene can be further enhanced, enriches the density of free carrier, and is provided
More electrochemical sites (DOI.org, 10.1016, j.carbon.2013.11.059), but the documents are logical
Peroxidating graphene and (NH4)2CO3Realization is reacted under hydro-thermal prepares nitrogen-doped graphene.Using hydro-thermal reaction, reproducibility compared with
Difference；In addition, hydro-thermal reaction carries out at high temperature under high pressure, (NH4)2CO3It decomposes and generates ammonia and carbon dioxide, will increase anti-
The pressure for answering kettle liner has certain danger.Meanwhile hydro-thermal reaction method low output, it is unfavorable for large-scale production and prepares material.
Invention content
The present invention uses positively charged supermolecule column [5] aromatic hydrocarbons, modifies electronegative redox graphene.Nitrogenous column
[5] aromatic hydrocarbons can be adsorbed on the surface of graphene oxide by electrostatic and pi-pi accumulation effect, to avoid graphene oxide layer
Stacking, be conducive to Si nano particles in the evenly dispersed of graphene sheet layer；Amorphous carbon layer, energy are coated in Si material surfaces
Volume expansion of Si nano particles during repeated charge is effectively relieved；The graphene of N doping has higher electrochemistry
Activity can further enhance the effect of lithium ion and graphene.The composite material shows high electrochemical lithium storage content and excellent
Different cycle performance.Silicon substrate composite negative pole material prepared by this method has potential application prospect in field of lithium ion battery.
The object of the present invention is to provide a kind of lithium ion battery negative materials with high power capacity and excellent cycling performance
Preparation method, specific process step are as follows：
(1) under stirring conditions, by water-soluble nitrogenous supermolecule column [5] aromatic hydrocarbons, (NSM, specific preparation method are shown in ginseng
Examine document DOI:10.1039/clccl5660h) be introduced into graphene oxide (GO) solution, obtain the oxidation of supermolecule modification
Graphene solution (NSM-GO)；
(2) nano silica fume is added to the water, after ultrasonic disperse is handled, is added in the mixed solution of step (1), continues
Ultrasonic disperse makes silica flour be dispersed in NSM-GO mixed solutions；Hydrazine hydrate is added and carries out Liquid reduction reaction process, products therefrom
It is dried after centrifugation, obtains the silicon materials of graphene support；Wherein hydrazine hydrate dosage is：5-15mL, preferably 10mL, liquid
Phase reduction reaction temperature is：60-100 DEG C, the time is：6-10h, liquid-phase reduction 8h at preferably 80 DEG C.
(3) silicon materials of the graphene support obtained to step (2) carry out carbon coating, and carbon coating process is chemical vapor deposition
Product cladding.The silicon materials for having adsorbed the graphene support of a small amount of nitrogenous column [5] aromatic hydrocarbons, in high temperature chemical vapor deposition carbon coated
In the process, it is converted to the carbon coating silicon substrate composite negative pole material of nitrogen-doped graphene support.
Nitrogen-doped graphene prepared by the present invention is by during high temperature chemical vapor deposition carbon coated while making
For what is obtained, reproducibility is preferable, is suitble to industrialization volume production, is with a wide range of applications in field of lithium ion battery.
Further, the structural formula of supermolecule column [5] aromatic hydrocarbons described in step (1) is as follows：
Its dosage is 0.015-0.15mmol.
Further, the molar ratio of the nano-silicon described in step (2) and graphene oxide is 0.1-1.
Further, the carbon coating process described in step (3) be liquid phase coating, chemical vapor deposition cladding in one kind or
More than one, preferably chemical vapor deposition coats, and the carbon source used in vapor deposition processes is acetylene gas/nitrogen, acetylene gas/argon
One kind in gas or acetylene gas/helium, temperature of plate are 500-1000 DEG C, and the cladding time is 1-12h.
The carbon coating silicon substrate composite negative pole material of nitrogen-doped graphene support prepared by the method for the present invention is used as lithium-ion electric
The negative material in pond.
Advantageous effect：
Beneficial effects of the present invention mainly have the following aspects：
(1) it uses supermolecule column [5] aromatic hydrocarbons to modify graphene oxide, can have to avoid the stacking of graphene oxide layer
Conducive to Si nano particles in the evenly dispersed of graphene sheet layer；
(2) graphene with excellent flexibility is combined in Si material surfaces cladding carbon-coating, in addition to Si materials can be improved
Electron conduction, moreover it is possible to the volumetric stress that silicon materials generate during lithium ion intercalation/deintercalation be effectively relieved, reduce Si materials
Cubical expansivity；
(3) graphene of nitrogen doped can realize the electron conduction further enhanced, enrich the close of free carrier
Degree, and the active sites of more electrochemical lithium storages are provided；
(4) the method for the present invention provides reference for application of the realization supermolecule in field of lithium ion battery.
Description of the drawings
Fig. 1 is protected using circulation volume when negative material is as lithium ion battery negative pole active materials made from embodiment 2
Holdup curve.
Specific implementation mode
To make those skilled in the art more fully understand technical scheme of the present invention, With reference to embodiment to the present invention
It is described in further detail.
It is prepared by graphene oxide solution:
By improved Hummers methods, commercial graphite powder is added in the concentrated sulfuric acid of 50mL, 30min is stirred by ultrasonic, is delayed
It is slow that 3.0g potassium permanganate is added, continue to stir 2h.Then the deionized water of 100mL is added, waits for that solution is cooled to room temperature addition
The hydrogen peroxide of 10mL 30%, continuously adds 200mL deionized waters stirring 1h, and centrifuge washing obtains graphene oxide solution.
Embodiment 1
0.015mmol columns [5] aromatic hydrocarbons is dissolved in 30mL deionized waters under stirring conditions, then proceedes to the item in stirring
It is added under part in the graphene oxide solution containing 1.2mol (30mL), stirs 2h, obtains the graphene oxide of supermolecule modification
Solution (NSM-GO).11.2g nano silica fumes are dispersed under conditions of ultrasound in 80mL deionized waters, NSM- is then added drop-wise to
In GO mixed solutions.Above mixed solution is transferred in the round-bottomed flask of 250mL, 10mL hydrazine hydrates are added, in stirring
Under the conditions of in 80 DEG C of back flow reaction 8h.The product of gained is collected by centrifugation, the silicon materials of graphene support are obtained after vacuum drying.On
The silicon materials for stating graphene support are put in tube furnace, are passed through nitrogen as protective gas, gas flow rate 200mL/min,
After being warming up to 800 DEG C, it is 1 to be passed through volume ratio:As carbon-coated carbon source, flow control is 10 acetylene/nitrogen mixed gas
40mL/min, the control cladding time is 6h at 800 DEG C.After deposition, the carbon coating silicon of nitrogen-doped graphene support is obtained
Base composite negative pole material.
Embodiment 2
0.06mmol columns [5] aromatic hydrocarbons is dissolved in 30mL deionized waters under stirring conditions, then proceedes to the item in stirring
It is added under part in the graphene oxide solution containing 1.2mol (30mL), stirs 2h, obtains the graphene oxide of supermolecule modification
Solution (NSM-GO).16.8g nano silica fumes are dispersed under conditions of ultrasound in 80mL deionized waters, NSM- is then added drop-wise to
In GO mixed solutions.Above mixed solution is transferred in the round-bottomed flask of 250mL, 10mL hydrazine hydrates are added, in stirring
Under the conditions of in 80 DEG C of back flow reaction 8h.The product of gained is collected by centrifugation, the silicon materials of graphene support are obtained after vacuum drying.On
The silicon materials for stating graphene support are put in tube furnace, are passed through nitrogen as protective gas, and gas flow rate is 200 mL/min,
After being warming up to 800 DEG C, it is 1 to be passed through volume ratio:As carbon-coated carbon source, flow control is 10 acetylene/nitrogen mixed gas
40mL/min, the control cladding time is 6h at 800 DEG C.After deposition, the carbon coating silicon of nitrogen-doped graphene support is obtained
Base composite negative pole material.
Fig. 1 is protected using circulation volume when negative material is as lithium ion battery negative pole active materials made from embodiment 2
Holdup curve.The data of Fig. 1 recycle when showing using negative material made from embodiment 2 as lithium ion battery negative pole active materials
Stability is good, and capacity retention ratio is still up to 91.9% after 150 cycles.Excellent stability is attributed to the carbon of Si material surfaces
The double protection of clad and graphene with excellent flexibility, be effectively relieved silicon materials be embedded in lithium ion/
Deviate from the volumetric stress generated in the process, reduces the cubical expansivity of Si materials, improve the cyclical stability of battery.
Embodiment 3
0.06mmol columns [5] aromatic hydrocarbons is dissolved in 30mL deionized waters under stirring conditions, then proceedes to the item in stirring
It is added under part in the graphene oxide solution containing 1.2mol (30mL), stirs 2h, obtains the graphene oxide of supermolecule modification
Solution (NSM-GO).16.8g nano silica fumes are dispersed under conditions of ultrasound in 80mL deionized waters, NSM- is then added drop-wise to
In GO mixed solutions.Above mixed solution is transferred in the round-bottomed flask of 250mL, 10mL hydrazine hydrates are added, in stirring
Under the conditions of in 80 DEG C of back flow reaction 8h.The product of gained is collected by centrifugation, the silicon materials of graphene support are obtained after vacuum drying.On
The silicon materials for stating graphene support are put in tube furnace, are passed through nitrogen as protective gas, and gas flow rate is 200 mL/min,
After being warming up to 700 DEG C, it is 1 to be passed through volume ratio:As carbon-coated carbon source, flow control is 10 acetylene/nitrogen mixed gas
40mL/min, the control cladding time is 6h at 700 DEG C.After deposition, the carbon coating silicon of nitrogen-doped graphene support is obtained
Base composite negative pole material.
Embodiment 4
0.03mmol columns [5] aromatic hydrocarbons is dissolved in 30mL deionized waters under stirring conditions, then proceedes to the item in stirring
It is added under part in the graphene oxide solution containing 1.2mol (30mL), stirs 2h, obtains the graphene oxide of supermolecule modification
Solution (NSM-GO).16.8g nano silica fumes are dispersed under conditions of ultrasound in 80mL deionized waters, NSM- is then added drop-wise to
In GO mixed solutions.Above mixed solution is transferred in the round-bottomed flask of 250mL, 10mL hydrazine hydrates are added, in stirring
Under the conditions of in 80 DEG C of back flow reaction 8h.The product of gained is collected by centrifugation, the silicon materials of graphene support are obtained after vacuum drying.On
The silicon materials for stating graphene support are put in tube furnace, are passed through nitrogen as protective gas, and gas flow rate is 200 mL/min,
After being warming up to 800 DEG C, it is 1 to be passed through volume ratio:As carbon-coated carbon source, flow control is 10 acetylene/nitrogen mixed gas
40mL/min, the control cladding time is 6h at 800 DEG C.After deposition, the carbon coating silicon of nitrogen-doped graphene support is obtained
Base composite negative pole material.
Embodiment 5
0.12mmol columns [5] aromatic hydrocarbons is dissolved in 30mL deionized waters under stirring conditions, then proceedes to the item in stirring
It is added under part in the graphene oxide solution containing 1.2mol (30mL), stirs 2h, obtains the graphene oxide of supermolecule modification
Solution (NSM-GO).22.4g nano silica fumes are dispersed under conditions of ultrasound in 80mL deionized waters, NSM- is then added drop-wise to
In GO mixed solutions.Above mixed solution is transferred in the round-bottomed flask of 250mL, 10mL hydrazine hydrates are added, in stirring
Under the conditions of in 80 DEG C of back flow reaction 8h.The product of gained is collected by centrifugation, the silicon materials of graphene support are obtained after vacuum drying.On
The silicon materials for stating graphene support are put in tube furnace, are passed through nitrogen as protective gas, and gas flow rate is 200 mL/min,
After being warming up to 500 DEG C, it is 1 to be passed through volume ratio:As carbon-coated carbon source, flow control is 10 acetylene/nitrogen mixed gas
40mL/min, the control cladding time is 8h at 500 DEG C.After deposition, the carbon coating silicon of nitrogen-doped graphene support is obtained
Base composite negative pole material.
Embodiment 6
0.12mmol columns [5] aromatic hydrocarbons is dissolved in 30mL deionized waters under stirring conditions, then proceedes to the item in stirring
It is added under part in the graphene oxide solution containing 1.2mol (30mL), stirs 2h, obtains the graphene oxide of supermolecule modification
Solution (NSM-GO).22.4g nano silica fumes are dispersed under conditions of ultrasound in 80mL deionized waters, NSM- is then added drop-wise to
In GO mixed solutions.Above mixed solution is transferred in the round-bottomed flask of 250mL, 10mL hydrazine hydrates are added, in stirring
Under the conditions of in 80 DEG C of back flow reaction 8h.The product of gained is collected by centrifugation, the silicon materials of graphene support are obtained after vacuum drying.On
The silicon materials for stating graphene support are put in tube furnace, are passed through nitrogen as protective gas, and gas flow rate is 200 mL/min,
After being warming up to 1000 DEG C, it is 1 to be passed through volume ratio:As carbon-coated carbon source, flow control is 10 acetylene/nitrogen mixed gas
40mL/min, the control cladding time is 6h at 1000 DEG C.After deposition, the carbon coating silicon of nitrogen-doped graphene support is obtained
Base composite negative pole material.
Comparative example 1
0.06mmol columns [5] aromatic hydrocarbons is dissolved in 30mL deionized waters under stirring conditions, then proceedes to the item in stirring
It is added under part in the graphene oxide solution containing 1.2mol (30mL), stirs 2h, obtains the graphene oxide of supermolecule modification
Solution (NSM-GO).16.8g nano silica fumes are dispersed under conditions of ultrasound in 80mL deionized waters, NSM- is then added drop-wise to
In GO mixed solutions.The above mixed solution is transferred in the round-bottomed flask of 250mL, 10mL hydrazine hydrates are added, in the item of stirring
In 80 DEG C of back flow reaction 8h under part.The product of gained is collected by centrifugation, the silicon materials of graphene support are obtained after vacuum drying.It is above-mentioned
The silicon materials of graphene support are put in tube furnace, are passed through nitrogen as protective gas, gas flow rate is 200 mL/min, is risen
Temperature keeps 6h to after 800 DEG C.Obtain the silicon substrate composite negative pole material of nitrogen-doped graphene support.
Comparative example 2
11.2g nano silica fumes are dispersed under conditions of ultrasound in 80mL deionized waters, are then added drop-wise to containing 1.2mol
Graphene oxide solution (60mL) in.Above mixed solution is transferred in the round-bottomed flask of 250mL, 10mL water is added
Hydrazine is closed, under stirring conditions in 80 DEG C of back flow reaction 8h.The product of gained is collected by centrifugation, graphene branch is obtained after vacuum drying
The silicon materials of support.The silicon materials of above-mentioned graphene support are put in tube furnace, are passed through nitrogen as protective gas, gas flow rate
For 200mL/min, after being warming up to 800 DEG C, it is 1 to be passed through volume ratio:10 acetylene/nitrogen mixed gas is as carbon-coated carbon
Source, flow control 40mL/min, the control cladding time is 6h at 800 DEG C.After deposition, the carbon of graphene support is obtained
Coat silicon substrate composite negative pole material.
It is prepared by negative plate：By weight using negative material obtained as active material and acetylene black, sodium carboxymethylcellulose
Than being 8:1:1 is uniformly mixed, and is coated on copper foil with automatic film applicator, the dry 12h at 80 DEG C, through twin rollers (pressure
15MPa) after roll-in, the sequin of a diameter of 16mm is cut into, working electrode is made.
Button cell assembles：Using metal lithium sheet as reference electrode, electrolyte is LiPF containing 1.0M6EC/DMC (v/v
=1/1) electrolyte, diaphragm use polyethylene diagrams, by anode cover, positive plate, diaphragm, lithium piece, nickel foam, no in glove box
Rust steel plate washer, negative plate sequence be assembled into button cell.
Battery testing：Using the chemical property of Wuhan indigo plant electrical testing system thinking button cell, charge-discharge magnification is
0.1C, charge voltage range 5mV-2.0V.The button prepared as negative material by the composite material of each embodiment and comparative example
The charge-discharge performance of formula battery the results are shown in Table 1.
1 embodiment of table and comparative example buckle electrical test results compared with
1 data result of table shows：The carbon coating silicon substrate supported using nitrogen-doped graphene prepared by the method for the present invention is compound
Negative material does not pass through carbon coating compared to comparative example, without the negative material that supermolecule participates in preparing, embodiment system
The carbon coating silicon substrate composite negative pole material of standby obtained nitrogen-doped graphene support show high power capacity, high coulombic efficiency for the first time and
Excellent cycle performance.
Claims (8)
1. a kind of preparation method of the carbon coating silicon substrate composite negative pole material of nitrogen-doped graphene support, it is characterised in that：It is described
Steps are as follows for preparation method：
(1) under stirring conditions, water-soluble nitrogenous supermolecule column [5] aromatic hydrocarbons (NSM) is introduced into graphene oxide (GO)
In solution, the graphene oxide mixed solution (NSM-GO) of supermolecule modification is obtained；
(2) nano silica fume is added to the water, after ultrasonic disperse is handled, is added in the mixed solution of step (1), continues ultrasound
Dispersion, makes silica flour be dispersed in NSM-GO mixed solutions；Then hydrazine hydrate is added and carries out Liquid reduction reaction process, gained is produced
Object is dried after centrifugation, obtains the silicon materials of graphene support；
(3) silicon materials of the graphene support obtained to step (2) carry out carbon coating, obtain the carbon packet of nitrogen-doped graphene support
Cover silicon substrate composite negative pole material.
2. the preparation method of the carbon coating silicon substrate composite negative pole material of nitrogen-doped graphene support as described in claim 1,
It is characterized in that：The dosage of supermolecule column [5] aromatic hydrocarbons described in step (1) is 0.015-0.15mmol.
3. the preparation method of the carbon coating silicon substrate composite negative pole material of nitrogen-doped graphene support as described in claim 1,
It is characterized in that：The molar ratio of nano-silicon and graphene oxide described in step (2) is 0.1-1.
4. the preparation method of the carbon coating silicon substrate composite negative pole material of nitrogen-doped graphene support as described in claim 1,
It is characterized in that：The dosage of hydrazine hydrate described in step (2) is 5-15mL, and Liquid reduction reaction process temperature is：60-100 DEG C, liquid phase is also
The former reaction time is：6-10h.
5. the preparation method of the carbon coating silicon substrate composite negative pole material of nitrogen-doped graphene support as claimed in claim 4,
It is characterized in that：The dosage of the hydrazine hydrate is 10mL, and Liquid reduction reaction process temperature is：80 DEG C, the Liquid reduction reaction process time is：
8h。
6. the preparation method of the carbon coating silicon substrate composite negative pole material of nitrogen-doped graphene support as described in claim 1,
It is characterized in that：Carbon coating process described in step (3) be liquid phase coating, one kind in chemical vapor deposition cladding or it is a kind of with
On.
7. the preparation method of the carbon coating silicon substrate composite negative pole material of nitrogen-doped graphene support as described in claim 1,
It is characterized in that：Carbon coating process described in step (3) coats for chemical vapor deposition, and carbon source used is acetylene gas/nitrogen, second
One kind in alkynes gas/argon gas or acetylene gas/helium, temperature of plate are 500-1000 DEG C, and the cladding time is 1-12h.
8. a kind of carbon coating silicon substrate composite negative pole material of nitrogen-doped graphene support prepared by method as described in claim 1
Using, it is characterised in that：The negative material is used as negative electrode of lithium ion battery.
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| CN109860567A (en) * | 2019-02-26 | 2019-06-07 | 成都爱敏特新能源技术有限公司 | A kind of Copper substrate graphene/silicon/carbon nitrogen combination electrode and preparation method thereof |
| CN111013579A (en) * | 2019-11-20 | 2020-04-17 | 珠海复旦创新研究院 | Limited-area carbon material loaded with palladium single atom or palladium nano-particles and preparation method thereof |
| CN113346060A (en) * | 2021-05-31 | 2021-09-03 | 广东工业大学 | Porous silicon/titanium dioxide/graphene composite material and preparation method and application thereof |
| CN114914410A (en) * | 2022-04-12 | 2022-08-16 | 广州大学 | Interface interaction for constructing built-in electric field for high-performance lithium ion storage |
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| CN109698335A (en) * | 2018-12-19 | 2019-04-30 | 扬州大学 | A kind of preparation method of column [5] aromatic hydrocarbons composite sulfur lithium sulphur positive electrode |
| CN109698335B (en) * | 2018-12-19 | 2021-09-17 | 扬州大学 | Preparation method of column [5] arene composite sulfur lithium sulfur positive electrode material |
| CN109860567A (en) * | 2019-02-26 | 2019-06-07 | 成都爱敏特新能源技术有限公司 | A kind of Copper substrate graphene/silicon/carbon nitrogen combination electrode and preparation method thereof |
| CN111013579A (en) * | 2019-11-20 | 2020-04-17 | 珠海复旦创新研究院 | Limited-area carbon material loaded with palladium single atom or palladium nano-particles and preparation method thereof |
| CN111013579B (en) * | 2019-11-20 | 2022-07-05 | 珠海复旦创新研究院 | Limited-area carbon material loaded with palladium single atom or palladium nano-particles and preparation method thereof |
| CN113346060A (en) * | 2021-05-31 | 2021-09-03 | 广东工业大学 | Porous silicon/titanium dioxide/graphene composite material and preparation method and application thereof |
| CN114914410A (en) * | 2022-04-12 | 2022-08-16 | 广州大学 | Interface interaction for constructing built-in electric field for high-performance lithium ion storage |
| CN114914410B (en) * | 2022-04-12 | 2024-04-12 | 广州大学 | Interface interaction construction of built-in electric field for high performance lithium ion storage |
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