CN109904391A - A kind of method of modifying and lithium metal battery of lithium metal battery cathode of lithium - Google Patents
A kind of method of modifying and lithium metal battery of lithium metal battery cathode of lithium Download PDFInfo
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- CN109904391A CN109904391A CN201910191376.8A CN201910191376A CN109904391A CN 109904391 A CN109904391 A CN 109904391A CN 201910191376 A CN201910191376 A CN 201910191376A CN 109904391 A CN109904391 A CN 109904391A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to electrode material and electrochemical fields, and in particular to a kind of method of modifying and lithium metal battery of lithium metal battery cathode of lithium.The present invention is by PVP K-30,1,3,5- benzenetricarboxylic acid and Ni (NO3)2·6H2O dissolves in methanol, stirring；Solvent thermal reaction is carried out later, the washed drying again of obtained sample；Obtained Ni-MOF presoma, then 300-500 DEG C under argon atmosphere at a temperature of kept for 2-4 hour, finally obtain Ni/C microballoon, material mixed with acetylene black, gum arabic coated on cathode of lithium.The present invention is surface modified modification to lithium metal battery cathode using the carbosphere of nickeliferous metal derived from Ni-MOF, and material shows high coulombic efficiency and excellent cyclical stability.
Description
Technical field
The present invention relates to electrode material and electrochemical fields, and in particular to a kind of method of modifying of lithium metal battery cathode of lithium
And lithium metal battery.
Background technique
As the snap informationization of society develops, the battery apparatus of exploitation higher energy density becomes ever more important.Lithium from
Sub- battery has biggish specific discharge capacity and volume and capacity ratio, thus becomes the one preferred technique of mainstream mancarried electronic aid.
Lithium an- ode is due to its theoretical specific capacity (3860 mAhg with superelevation-1), it is Standard graphite cathode (370 mAhg-1)
More than ten times, and lithium metal has minimum negative electricity chemical potential (- 3.04V), and become the hot spot of research.But lithium metal
Cathode easily forms the irreversible reaction of irregular Li dendrite and cathode of lithium and organic electrolyte during the deposition process, and causing can not
Inverse capacitance loss, so that cycle performance fails rapidly, this causes its coulombic efficiency low, and cyclical stability and safety are poor.One
Aspect, the Li dendrite of generation are easy to fall off and form " dead lithium ", not only reduce the coulombic efficiency of battery and exacerbate pair
The generation of reaction.On the other hand, the Li dendrite of formation easily pierces through diaphragm and causes internal short-circuit, or even on fire or explosion occurs
Etc. safety accidents.To solve the above-mentioned problems, researchers at home and abroad have made a large amount of modified work to this, and exploitation is able to suppress
The method and associated materials of lithium dendrite growth are the research hotspot and emphasis in the current field.
Patent CN108550821A discloses a kind of core-shell structure phosphatization nickel carbon (Ni based on Ni-MOF2P/C) microballoon
Preparation method belongs to field of lithium ion battery cathode material preparation.Preparation method is to utilize organic ligand and nickel salts system
Standby spherical shape nickel based metal organic frame compound (Ni-MOF) presoma, obtains core-shell structure by high temperature cabonization and low temperature phosphor
Ni2P/C microballoon shows high coulombic efficiency for the first time, biggish specific volume when the electrode material is used as negative electrode of lithium ion battery
The features such as amount, excellent high rate performance and stable long circulating performance；Preparation method is simple and easy, it is low in cost, it can be achieved that
Large-scale production, but the application in lithium ion battery is entirely different with the application in lithium metal battery.
Using the material of embeddable lithium ion, (negative electrode material is commercialized stone to positive and negative pole material in lithium ion battery
Ink and Li4TiO12, transition metal oxide, sulfide and phosphide etc. can also do cathode, but not have commercialization also at present).
Lithium metal battery, which is that cathode is fixed, does active material using metal Li, can be direct metal lithium solid or is generated by electro-deposition
Lithium metal and its compound etc..Typically directly using lithium metal since the generation of Li dendrite is unsafe, so must be through
Cross the Land use systems for improving lithium metal.
The invention is the Ni with synthesis2P/C microballoon is applied to lithium ion battery as negative electrode material, is primarily involved in electrochemistry
The active material of reaction is Ni2P, the conversion reaction that this material uses store lithium ion.The present invention is that synthetic surface uniformly divides
The Ni/C micro-sphere material of the W metal of cloth, emphasis adjust the nucleation of plating metal lithium using uniform Ni small metal particles
Journey, the lithium metal of Li dendrite and the material of Ni/C microballoon will not be generated in electroplating deposition and course of dissolution by preparing metal.Institute
Ni/C micro-sphere material is the carrier of bearing metal lithium, itself does not have electro-chemical activity.
Summary of the invention
The purpose of the present invention is to provide the method for modifying and lithium metal battery of a kind of lithium metal battery cathode of lithium.The present invention
The carbosphere of nickeliferous metal derived from a kind of Ni-MOF of preparation is surface modified modification, material to lithium metal battery cathode
Show high coulombic efficiency and excellent cyclical stability.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of method of modifying of lithium metal battery cathode of lithium, comprising the following steps:
(1) preparation of nickel carbosphere Ni/C: by 300-600mg PVP K-30,150-200mg 1,3,5- benzene three
Formic acid and 200-300mgNi (NO3)2·6H2O is dissolved in the methanol of 20-50 ml, stirs 5-10min；It later will be molten equipped with this
The stainless steel autoclave that the polytetrafluoroethylene (PTFE) of liquid does liner is put into baking oven, and 150-200 DEG C of constant temperature 8-12h, obtained sample is again
It cleans 3-5 times through methanol, is then dried at 60 DEG C；Ni-MOF presoma is obtained, finally by Ni-MOF presoma in argon
Under atmosphere is enclosed, 2-4 hour is kept at a temperature of 300-500 DEG C, finally obtains Ni/C microballoon.
(2) lithium metal battery is modified: according to the Ni/C microballoon of mass ratio: acetylene black: gum arabic=60-80:10-20:10-
1.2 cm are equably coated in after 20 mixed grindings2Copper sheet on work electrode.
A kind of lithium metal battery for the cathode of lithium that the method for modifying obtains, with electrode of working on modified copper sheet,
Lithium metal is used as to electrode, and electrolyte is the ethylene glycol dimethyl ether solution of (trimethyl fluoride sulfonyl) imine lithium of 1.0M bis- LiTFSI；
Battery assembly carries out in glove box under protection of argon gas, and oxygen and moisture content are below 1ppm in the glove box.
Remarkable advantage of the invention is:
Application the present invention provides a kind of carbosphere of nickeliferous metal derived from Ni-MOF as lithium metal battery cathode.Material
Show high coulombic efficiency and excellent cyclical stability.Its is at low cost, with high purity, has excellent performance, and can largely synthesize.This
One invention has excellent application prospect in cheap high-performance lithium metal battery.
Detailed description of the invention
The XRD diagram of Fig. 1 nickel carbosphere material；
The high power and low power scanning electron microscope (SEM) photograph of Fig. 2 nickel carbosphere material；
The nucleation overpotential comparison diagram of Fig. 3 nickel carbosphere material and commercialization copper foil；
The coulombic efficiency comparison diagram of Fig. 4 nickel carbosphere material and commercialization copper foil.
Specific embodiment
Further to disclose rather than the present invention is limited, the present invention is described in further detail below in conjunction with example.
Embodiment 1
A kind of method of modifying and lithium metal battery preparation of lithium metal battery cathode of lithium, comprising the following steps:
(1) preparation of nickel carbosphere Ni/C: by 300mg PVP K-30,150mg 1,3,5- benzenetricarboxylic acid and
200mgNi(NO3)2·6H2O is dissolved in the methanol of 20 ml, stirs 5min；The polytetrafluoroethylene (PTFE) equipped with the solution is done later
The stainless steel autoclave of liner is put into baking oven, 150 DEG C of constant temperature 8h, and obtained sample cleans 3 times through methanol again, then at 60 DEG C
Lower drying；Ni-MOF presoma has been obtained, finally by Ni-MOF presoma under argon atmosphere, has kept 2 at a temperature of 450 DEG C
A hour finally obtains Ni/C microballoon.
(2) lithium metal battery assembles: Ni/C microballoon: acetylene black: equably applying after gum arabic=75:15:15 mixed grinding
In 1.2 cm2Copper sheet on do cathode, lithium metal is used as to electrode, and electrolyte is that the glycol dimethyl ether of 1.0M LiTFSI is molten
Liquid；Battery assembly carries out (oxygen and moisture content are below 1ppm) in glove box under protection of argon gas.
Embodiment 2
A kind of method of modifying and lithium metal battery preparation of lithium metal battery cathode of lithium, comprising the following steps:
(1) preparation of nickel carbosphere Ni/C: by 450mg PVP K-30,175mg 1,3,5- benzenetricarboxylic acid and
250mgNi(NO3)2·6H2O is dissolved in the methanol of 35 ml, stirs 7min；The polytetrafluoroethylene (PTFE) equipped with the solution is done later
The stainless steel autoclave of liner is put into baking oven, 170 DEG C of constant temperature 10h, and obtained sample cleans 4 times through methanol again, then 60
It is dried at DEG C；Ni-MOF presoma has been obtained, finally by Ni-MOF presoma under argon atmosphere, has been protected at a temperature of 500 DEG C
2 hours are held, Ni/C microballoon is finally obtained.
(2) lithium metal battery assembles: Ni/C microballoon: acetylene black: equably applying after gum arabic=80:10:10 mixed grinding
In 1.2 cm2Copper sheet on do cathode, lithium metal is used as to electrode, and electrolyte is that the glycol dimethyl ether of 1.0M LiTFSI is molten
Liquid；Battery assembly carries out (oxygen and moisture content are below 1ppm) in glove box under protection of argon gas.
Embodiment 3
A kind of method of modifying and lithium metal battery preparation of lithium metal battery cathode of lithium, comprising the following steps:
(1) preparation of nickel carbosphere Ni/C: by 600mg PVP K-30,200mg 1,3,5- benzenetricarboxylic acid and
300mgNi(NO3)2·6H2O is dissolved in the methanol of 50 ml, stirs 10min；The polytetrafluoroethylene (PTFE) of the solution will be housed later
The stainless steel autoclave for doing liner is put into baking oven, 190 DEG C of constant temperature 12h, and obtained sample cleans 5 times through methanol again, is then existed
It is dried at 60 DEG C；Ni-MOF presoma is obtained, finally by Ni-MOF presoma under argon atmosphere, at a temperature of 500 DEG C
It is kept for 3 hours, finally obtains Ni/C microballoon.
(2) lithium metal battery assembles: Ni/C microballoon: acetylene black: being equably coated in after gum arabic=80:15:5 mixed grinding
1.2 cm2Copper sheet on do cathode, lithium metal is used as to electrode, and electrolyte is the ethylene glycol dimethyl ether solution of 1.0M LiTFSI；
Battery assembly carries out (oxygen and moisture content are below 1ppm) in glove box under protection of argon gas.
The nickel carbosphere composite material that the present invention designs preparation can be obviously improved cyclical stability.Fig. 1 is Ni/C material
XRD diagram, as can be seen from the figure the material contains two kinds of substances of Ni metal and C.Fig. 2 is that the SEM of Ni/C material schemes, Cong Tuzhong
As can be seen that material is shaggy uniform carbosphere, the diameter of microballoon is about 500-800 ran, Ni gold
Belong to nanoparticle to be uniformly embedded on carbosphere, metal nanoparticle size is about 5-10 nanometers, these Ni metal nanos
Particle is capable of the deposition of Effective Regulation lithium metal.As shown in figure 3, nickel carbosphere composite material is than commercialization copper foil with smaller
It is nucleated overpotential, talks about its good close lithium.As shown in figure 4, be the coulombic efficiency figure of nickel carbosphere metal negative electrode material, from
In figure as can be seen that after circulation 100 times, still there is stable high coulombic efficiency (98% or more), and be commercialized copper foil warp
It crosses after 50 times with regard to rapid decay.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (6)
1. a kind of method of modifying of lithium metal battery cathode of lithium, it is characterised in that: using nickeliferous metal derived from a kind of Ni-MOF
Carbosphere modification is surface modified to lithium metal battery cathode.
2. a kind of method of modifying of lithium metal battery cathode of lithium according to claim 1, it is characterised in that:
Specifically includes the following steps:
(1) preparation of nickel carbosphere Ni/C: by 300-600mg PVP K-30,150-200mg 1,3,5- benzene three
Formic acid and 200-300mgNi (NO3)2·6H2O is dissolved in the methanol of 20-50 ml, stirs 5-10min；It later will be molten equipped with this
The stainless steel autoclave that the polytetrafluoroethylene (PTFE) of liquid does liner is put into baking oven, carries out solvent thermal reaction, obtained sample is again through first
Alcohol cleans 3-5 times, then dries at 60 DEG C；Ni-MOF presoma is obtained, finally by Ni-MOF presoma in argon atmospher
Under enclosing, calcining finally obtains Ni/C microballoon.
(2) lithium metal battery is modified: according to mass ratio Ni/C microballoon: acetylene black: gum arabic=60-80:10-20:10-20
1.2 cm are equably coated in after mixed grinding2Copper sheet on do cathode.
3. a kind of method of modifying of lithium metal battery cathode of lithium according to claim 2, it is characterised in that: step (1) institute
Stating solvent thermal reaction condition is specially 150-200 DEG C of constant temperature 8-12h.
4. a kind of method of modifying of lithium metal battery cathode of lithium according to claim 2, it is characterised in that: step (1) institute
State calcination condition are as follows: 2-4 hour is kept at a temperature of 300-500 DEG C.
5. a kind of lithium metal battery of the cathode of lithium obtained based on any one of Claims 1 to 4 method of modifying, feature are existed
In: to do cathode on modified copper sheet, lithium metal is used as to electrode, and electrolyte is 1.0M bis- (trimethyl fluoride sulfonyl) imines
The ethylene glycol dimethyl ether solution of lithium LiTFSI；Battery assembly carries out in glove box under protection of argon gas.
6. a kind of lithium metal battery according to claim 5, it is characterised in that: oxygen and moisture content in the glove box
It is below 1ppm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111063549A (en) * | 2019-12-23 | 2020-04-24 | 南京农业大学 | Two-dimensional MOFs nanosheet-derived full-electrode material for hybrid capacitor |
| CN112265979A (en) * | 2020-11-02 | 2021-01-26 | 福建师范大学 | Preparation method of hollow octahedral carbon cage used as negative electrode material of potassium ion battery |
| CN114005960A (en) * | 2021-10-22 | 2022-02-01 | 长兴太湖能谷科技有限公司 | Lithium metal composite strip capable of inhibiting dendritic crystal growth of lithium battery |
| CN114744162A (en) * | 2022-06-09 | 2022-07-12 | 中博龙辉装备集团股份有限公司 | Nickel-modified nitrogen-doped porous carbon lithium-loaded negative electrode and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111063549A (en) * | 2019-12-23 | 2020-04-24 | 南京农业大学 | Two-dimensional MOFs nanosheet-derived full-electrode material for hybrid capacitor |
| CN111063549B (en) * | 2019-12-23 | 2021-05-18 | 南京农业大学 | Two-dimensional MOFs nanosheet-derived full-electrode material for hybrid capacitor |
| CN112265979A (en) * | 2020-11-02 | 2021-01-26 | 福建师范大学 | Preparation method of hollow octahedral carbon cage used as negative electrode material of potassium ion battery |
| CN114005960A (en) * | 2021-10-22 | 2022-02-01 | 长兴太湖能谷科技有限公司 | Lithium metal composite strip capable of inhibiting dendritic crystal growth of lithium battery |
| CN114005960B (en) * | 2021-10-22 | 2023-10-27 | 长兴太湖能谷科技有限公司 | Lithium metal composite strip capable of inhibiting dendrite growth of lithium battery |
| CN114744162A (en) * | 2022-06-09 | 2022-07-12 | 中博龙辉装备集团股份有限公司 | Nickel-modified nitrogen-doped porous carbon lithium-loaded negative electrode and preparation method and application thereof |
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Application publication date: 20190618 |