CN109841828A - A kind of lithium anode and preparation method thereof of body phase micro-nano structure - Google Patents
A kind of lithium anode and preparation method thereof of body phase micro-nano structure Download PDFInfo
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- CN109841828A CN109841828A CN201910094507.0A CN201910094507A CN109841828A CN 109841828 A CN109841828 A CN 109841828A CN 201910094507 A CN201910094507 A CN 201910094507A CN 109841828 A CN109841828 A CN 109841828A
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Abstract
The present invention discloses a kind of lithium anode preparation method of body phase micro-nano structure, realizes that stablizing for lithium anode recycles by body phase micro-nano structure, the specific steps are first by by heating lithium metal to molten condition；Secondly, different content metal or metal oxide are added into molten metal lithium, after being sufficiently mixed stirring；Finally, it is cooled to room temperature to obtain body phase micro-nano structure lithium metal.Body phase micro-nano structure lithium metal of the invention is made of the lithium metal particle of micron or nanostructure, and the volume fluctuation problem of lithium metal can be effectively relieved.Compared to common metal lithium, the lithium anode of micro-nano structure has certain anti-powdering characteristic.The lithium metal of body phase micro-nano structure shows more quick ionic conduction characteristic due to existing with more crystal boundaries.Meanwhile the lithium metal of body phase micro-nano structure has good cyclical stability, in the deposition course of dissolution of lithium metal, structure will not occur significantly to change, and can satisfy the macrocyclic demand of battery.
Description
Technical field
The present invention relates to high energy storage lithium metal battery technical field, the lithium metal for specifically designing a kind of body phase micro-nano structure is negative
Pole and preparation method thereof.
Background technique
Currently, the lithium ion battery specific energy of commercialization is difficult to continue to improve already close to theoretical capacity, therefore develop tool
The battery of more height ratio capacity is the hot spot studied at present.Lithium anode is due to high theoretical capacity, low electrochemistry
The advantages that current potential and light density and be considered as ideal lithium cell negative pole material.However due to Li dendrite problem and it is present in
Lasting side reaction between lithium metal and electrolyte causes the application of lithium metal battery to be constantly subjected to limit.
Li dendrite is the dendritic lithium deposit occurred in Multiple depositions/course of dissolution due to lithium metal.Dendrite is raw
Length can bring the problem of two aspects: (1) dendrite, which can pierce through diaphragm, leads to battery short circuit, and the short circuit current inside positive and negative anodes is in electricity
Heat inside pond causes battery system thermal runaway, and then causes a series of safety problems such as batteries caught fire even explosion；(2) branch
Crystalline substance will increase the side reaction of electrolyte and lithium metal, consume lithium active material, reduce battery utilization rate.It is detached from the lithium branch of collector
Crystalline substance is dead lithium, and the appearance of dead lithium can reduce available active material, reduce the efficiency and cycle life of battery.In addition it is worth
It is noted that all electrode materials can all undergo volume change during charge and discharge cycles, or even connect commercialized stone
Electrode ink also has 10% volume change.And for lithium metal, since it does not have carrier material, volume change is then bigger.
From a practical point of view, the face amount of unilateral commercial electrode needs to reach 3mAh cm-2, 14.6 μm will be had for lithium
Volume change.This numerical value is in the future may can also be bigger, it is meant that the movement at lithium interface will reach in cyclic process
Tens microns.This volume change is totally unfavorable for stablizing solid liquid interface (SEI), will cause the lasting consumption of electrolyte,
And then seriously affect the cycle life of battery.In addition, huge volume change also results in the generation of electrode powder phenomenon-tion, promote
Side reaction further increases and the generation of more dead lithiums.
Therefore, the enormousness variation for how alleviating lithium metal avoids causing electrode powder occur since enormousness changes
Change and the generation (especially charge status under high current) of a large amount of inert matters are to determine that can lithium anode be realized
The key of application.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of lithium anode of body phase micro-nano structure and
Preparation method, by construct phase micro-nano structure lithium anode, the stability that can well solve lithium anode is asked
Topic.More particularly to metal or metal oxide are added in molten metal lithium, then pass through certain cooling technique, obtain body phase
The lithium anode of micro-nano structure.Purpose is that the volume fluctuation of lithium metal can not only be effectively relieved by this micro-nano structure to ask
Topic, while body phase micro-nano structure lithium metal can be effectively improved ion/electron-transport in lithium metal deposition/course of dissolution, mention
The response speed for rising electrode reaction is the high rate performance for improving lithium anode.
Compared with the existing technology, the invention has the characteristics that: body phase micro-nano structure lithium metal of the invention by micron or
The lithium metal particle of nanostructure forms, and the volume fluctuation problem of lithium metal can be effectively relieved.Compared to common metal lithium, micro-nano
The lithium anode of structure has certain anti-powdering characteristic.The lithium metal of body phase micro-nano structure with more crystal boundaries due to depositing
, therefore show more quick ionic conduction characteristic.Meanwhile the lithium metal of body phase micro-nano structure has good circulation
Stability, in the deposition course of dissolution of lithium metal, structure will not occur significantly to change, and can satisfy the macrocyclic need of battery
It asks.
As a kind of lithium anode of body phase micro-nano structure of the present invention, the body phase micro-nano structure lithium metal is to pass through
By heating lithium metal to molten condition, different content metal or metal oxide are then added into molten metal lithium, it is sufficiently mixed
After closing stirring, it is cooled to room temperature to obtain body phase micro-nano structure lithium metal.
As a kind of lithium anode of body phase micro-nano structure of the present invention, the metal or metal oxide be aluminium oxide,
One of calcium oxide, bismuth oxide, tin oxide, zinc oxide, silica, boron oxide are a variety of, and the size of metal oxide is 10
~10000nm.
The content of metal or metal oxide is 1%~35%.
As a kind of lithium anode of body phase micro-nano structure of the present invention, the cooling velocity of the molten metal lithium is 1
℃min-1~400 DEG C of min-1。
As a kind of lithium anode of body phase micro-nano structure of the present invention, the lithium anode is in deposition/dissolution one
Without apparent powder phenomenon-tion after fixing turn, deposition/dissolution working current density is in 100 μ A cm-2~50mA cm-2Between.
Beneficial effect
By the lithium anode in construct phase micro-nano structure, cyclical stability is greatly improved.Right
Claim in battery testing, all electrolyte are esters electrolyte, compared to conventional lithium foil electrode, are occurred after circulation 50 encloses number obvious
Powder phenomenon-tion, and the lithium anode of body phase micro-nano structure circulation 100 circle after, still without apparent powder phenomenon-tion send out
It is raw.In addition, the lithium anode of body phase micro-nano structure is due to having quick ion/electronics conductive advantages, in high current density
(10mA cm-2) under the conditions of deposition/dissolution, equally show good cyclical stability.
Compared to conventional metals cathode of lithium, body phase micro-nano structure lithium metal due to excellent dynamics transmission characteristic and
Lesser electrode volume variation, to show more excellent cyclical stability and certain anti-powdering characteristic.
Detailed description of the invention
Fig. 1 is the preparation flow figure of bulk metal lithium electrode.
The tin matrix phase lithium metal that Fig. 2 is prepared.
Fig. 3 silicon substrate bulk metal and pure metal lithium recycle the interface impedance map after different circle numbers.
Specific embodiment
A kind of body phase micro-nano structure lithium anode provided by the invention, it is characterised in that by adding into molten metal lithium
Enter metal oxide, then obtains the bulk metal lithium with micro-nano structure by stirring cooling.
The present invention is further explained in the light of specific embodiments.
Embodiment 1
In the present embodiment by the way that oxidation is then added into molten lithium by heating lithium metal to molten condition (400 DEG C)
Silicon (mean size of silicon oxide particle is 600nm or so, silica content 5%), it is stirring while adding, it mixes them thoroughly,
Then cooled to room temperature to get arrive body phase micro-nano structure lithium metal.Then, the body Xiang Wei that will be obtained by the method for rolling piece
Micro-nano structure lithium metal rolls slabbing, then by blunderbuss cuts to obtain pole piece spare.As shown in Figure 1.
Embodiment 2
In the present embodiment by the way that oxidation is then added into molten lithium by heating lithium metal to molten condition (400 DEG C)
Zinc (mean size of Zinc oxide particles is 10nm or so, content 35%), it is stirring while adding, it mixes them thoroughly, then 10
℃ min-1It is cooled to room temperature to get body phase micro-nano structure lithium metal is arrived.Then, the body Xiang Wei that will be obtained by the method for rolling piece
Micro-nano structure lithium metal rolls slabbing, then by blunderbuss cuts to obtain pole piece spare.
Embodiment 3
In the present embodiment by the way that oxidation is then added into molten lithium by heating lithium metal to molten condition (400 DEG C)
Bismuth (mean size of Bismuth oxide particles is 300nm or so, oxidation bi content be 15%), it is stirring while adding, mix them thoroughly,
Then 400 DEG C of min-1It is cooled to room temperature to get body phase micro-nano structure lithium metal is arrived.Then, it will be obtained by rolling the method for piece
Body phase micro-nano structure lithium metal rolls slabbing, then by blunderbuss cuts to obtain pole piece spare.
Embodiment 4
In the present embodiment by the way that oxidation is then added into molten lithium by heating lithium metal to molten condition (400 DEG C)
Tin (mean size of granules of stannic oxide be 1 μm or so, oxidation Theil indices be 10%), it is stirring while adding, mix them thoroughly, so
1 DEG C of min afterwards-1It is cooled to room temperature to get body phase micro-nano structure lithium metal is arrived, as shown in Figure 2.It then, will by rolling the method for piece
Obtained body phase micro-nano structure lithium metal rolls slabbing, then by blunderbuss cuts to obtain pole piece spare.
Embodiment 5
In the present embodiment by the way that oxidation is then added into molten lithium by heating lithium metal to molten condition (400 DEG C)
Calcium (mean size of calcium oxide particle is 10 μm or so, calcium oxide content 1%), it is stirring while adding, it mixes them thoroughly, so
20 DEG C of min afterwards-1It is cooled to room temperature to get body phase micro-nano structure lithium metal is arrived, as shown in Figure 2.Then, the method by rolling piece
Obtained body phase micro-nano structure lithium metal is rolled into slabbing, then by blunderbuss cuts to obtain pole piece spare.
Embodiment 6
In the present embodiment by the way that oxidation is then added into molten lithium by heating lithium metal to molten condition (400 DEG C)
Aluminium (mean size of alumina particle is 2 μm or so, alumina content 11%), it is stirring while adding, it mixes them thoroughly, so
100 DEG C of min afterwards-1It is cooled to room temperature to get body phase micro-nano structure lithium metal is arrived, as shown in Figure 2.Then, the method by rolling piece
Obtained body phase micro-nano structure lithium metal is rolled into slabbing, then by blunderbuss cuts to obtain pole piece spare.
Embodiment 7
In the present embodiment by the way that oxidation is then added into molten lithium by heating lithium metal to molten condition (400 DEG C)
Boron (mean size of boron oxide granule is 300nm or so, boron oxide content 3%), it is stirring while adding, it mixes them thoroughly,
Then 35 DEG C of min-1It is cooled to room temperature to get body phase micro-nano structure lithium metal is arrived, as shown in Figure 2.Then, by rolling the side of piece
Obtained body phase micro-nano structure lithium metal is rolled slabbing by method, then by blunderbuss cuts to obtain pole piece spare.
Embodiment 8
In the glove box full of argon gas, using body phase micro-nano structure lithium anode or common metal lithium as cathode, adopt
With 2325 diaphragm of Celgard, lithium metal dresses up button cell as reference electrode and to electrode.Electrolyte used in the present invention
Include certain density lithium salts and organic solvent.Lithium salts is respectively lithium hexafluoro phosphate, solvent ethylene carbonate and diethyl carbonate.
It is carried out depositing/dissolution experiment with blue electricity.Test current density are as follows: 100 μ A cm-2.It is only capable of recycling compared to common metal lithium electrode
There is significant voltage fluctuation in 60 circles, body phase micro-nano structure lithium anode can have been still maintained after the circle of circulation 200 compared with
Good stability.
Embodiment 9
In the glove box full of argon gas, using body phase micro-nano structure lithium anode or common metal lithium as cathode, adopt
With 2325 diaphragm of Celgard, lithium metal dresses up button cell as reference electrode and to electrode.Electrolyte used in the present invention
Include certain density lithium salts and organic solvent.Lithium salts is respectively lithium hexafluoro phosphate, solvent ethylene carbonate and diethyl carbonate.
AC impedance experiment is carried out with electrochemical workstation.Acquired results are as shown in Figure 3.
Embodiment 10
By the battery after multiple circulation, is dismantled in glove box, cathode is rinsed and dries processing, is swept with cold field emission
Retouch electron microscope (SEM) observation lithium metal deposition morphology.Compared to lithium foil electrode, bulk metal lithium shows certain anti-powder
Change characteristic, and high rate performance is also more excellent.
Embodiment 11
Bulk metal lithium or lithium foil are as cathode, LiFePO4As anode, it is assembled into button cell and carries out full battery survey
Examination, positive and negative anodes capacity match by a certain percentage, and electrolyte lithium salts used is lithium hexafluoro phosphate, and solvent is ethylene carbonate/carbonic acid
Diethylester.Compared to lithium foil electrode, bulk metal lithium shows more excellent high rate performance.
Embodiment 12
In the present embodiment by the way that metallic sodium is heated to molten condition (300 DEG C), quartz is then added into molten lithium
(mean size of quartz particles is 200nm or so, quartz content 5%), it is stirring while adding, it mixes them thoroughly, then certainly
It is so cooled to room temperature to get body phase micro-nano structure metallic sodium is arrived.Then, the body phase micro-nano structure that will be obtained by the method for rolling piece
Metallic sodium rolls slabbing, then by blunderbuss cuts to obtain pole piece spare.
Embodiment 13
Bulk metal sodium or sodium piece are as cathode, Na3V2(PO4)4As anode, it is assembled into button cell and carries out full battery
Test, positive and negative anodes capacity match by a certain percentage, and electrolyte lithium salts used is sodium hexafluoro phosphate, and solvent is ethylene carbonate/carbon
Diethyl phthalate.Compared to sodium plate electrode, body phase micro-nano metallic sodium shows more excellent high rate performance.
In conclusion passing through the lithium metal of construct phase micro-nano structure, the cyclical stability of lithium metal can be significantly improved,
And inhibit the generation of lithium metal powder phenomenon-tion to a certain extent.This method simple possible, it is at low cost, it is suitable for large-scale application.
Above content is merely a preferred embodiment of the present invention, and is not intended to limit embodiment of the present invention, and this field is general
Logical technical staff's central scope according to the present invention and spirit can very easily carry out corresponding flexible or modification, therefore
Protection scope of the present invention should be subject to protection scope required by claims.
Claims (5)
1. a kind of lithium anode preparation method of body phase micro-nano structure, characterized in that realize metal by body phase micro-nano structure
Cathode of lithium stablizes circulation,
1) by by heating lithium metal to molten condition；
2) different content metal or metal oxide are added into molten metal lithium, after being sufficiently mixed stirring；
3) it is cooled to room temperature to obtain body phase micro-nano structure lithium metal.
2. a kind of lithium anode preparation method of body phase micro-nano structure according to claim 1, characterized in that described
Metal oxide is one of aluminium oxide, calcium oxide, bismuth oxide, tin oxide, zinc oxide, silica, boron oxide or a variety of, gold
Belong to or the particle size of metal oxide is 10~10000nm.
3. a kind of lithium anode preparation method of body phase micro-nano structure according to claim 1 or 2, characterized in that institute
The content for stating metal or metal oxide is 1%~35%.
4. a kind of lithium anode preparation method of body phase micro-nano structure according to claim 1, characterized in that described cold
But speed is 1 DEG C of min-1~400 DEG C of min-1。
5. lithium anode according to claim 1, characterized in that the lithium anode is not bright after deposition/dissolution
Aobvious powder phenomenon-tion, deposition/dissolution working current density is in 100 μ A cm-2~50mA cm-2Between.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111952575A (en) * | 2020-08-22 | 2020-11-17 | 浙江理工大学 | Inorganic Si-ZnO-Li composite material, preparation method and application thereof in lithium metal battery |
| CN112103472A (en) * | 2019-06-17 | 2020-12-18 | 上海汽车集团股份有限公司 | Metal lithium composite material and preparation method thereof |
| CN113506872A (en) * | 2021-06-25 | 2021-10-15 | 南京同宁新材料研究院有限公司 | Lithium metal negative electrode material and preparation method and application thereof |
| CN113809390A (en) * | 2021-07-30 | 2021-12-17 | 福建巨电新能源股份有限公司 | Preparation method of composite negative electrode of lithium battery |
| CN113871597A (en) * | 2021-09-27 | 2021-12-31 | 电子科技大学长三角研究院(湖州) | Lithium composite negative electrode material with three-dimensional framework structure and reserved space on surface and preparation method thereof |
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| CN108461724A (en) * | 2018-03-05 | 2018-08-28 | 苏州大学 | A kind of preparation method of high security metal composite negative pole |
| CN108511708A (en) * | 2018-03-14 | 2018-09-07 | 清华大学 | A kind of solid composite metal cathode of lithium |
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Patent Citations (2)
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| CN108461724A (en) * | 2018-03-05 | 2018-08-28 | 苏州大学 | A kind of preparation method of high security metal composite negative pole |
| CN108511708A (en) * | 2018-03-14 | 2018-09-07 | 清华大学 | A kind of solid composite metal cathode of lithium |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112103472A (en) * | 2019-06-17 | 2020-12-18 | 上海汽车集团股份有限公司 | Metal lithium composite material and preparation method thereof |
| CN111952575A (en) * | 2020-08-22 | 2020-11-17 | 浙江理工大学 | Inorganic Si-ZnO-Li composite material, preparation method and application thereof in lithium metal battery |
| CN111952575B (en) * | 2020-08-22 | 2022-06-28 | 浙江理工大学 | Inorganic Si-ZnO-Li composite material, preparation method and application thereof in lithium metal battery |
| CN113506872A (en) * | 2021-06-25 | 2021-10-15 | 南京同宁新材料研究院有限公司 | Lithium metal negative electrode material and preparation method and application thereof |
| CN113809390A (en) * | 2021-07-30 | 2021-12-17 | 福建巨电新能源股份有限公司 | Preparation method of composite negative electrode of lithium battery |
| CN113871597A (en) * | 2021-09-27 | 2021-12-31 | 电子科技大学长三角研究院(湖州) | Lithium composite negative electrode material with three-dimensional framework structure and reserved space on surface and preparation method thereof |
| CN113871597B (en) * | 2021-09-27 | 2023-11-10 | 电子科技大学长三角研究院(湖州) | Lithium composite anode material with three-dimensional framework structure and reserved space on surface and preparation method thereof |
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Application publication date: 20190604 |