CN107492650A - A kind of composite for Anode of lithium cell and preparation method thereof - Google Patents
A kind of composite for Anode of lithium cell and preparation method thereof Download PDFInfo
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- CN107492650A CN107492650A CN201710747681.1A CN201710747681A CN107492650A CN 107492650 A CN107492650 A CN 107492650A CN 201710747681 A CN201710747681 A CN 201710747681A CN 107492650 A CN107492650 A CN 107492650A
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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
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
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Abstract
The invention discloses a kind of composite for Anode of lithium cell and preparation method thereof.The composite is by cupric oxide, W2O3It is compounded to form with C three, cupric oxide is equably arranged in opper matrix of sufficient porosity surface, piece thickness about 20 35nm, W of cupric oxide nano blade in three dimendional blade shape2O3The surface of cupric oxide is coated on C, on the basis of the three-dimensional architecture of cupric oxide nano blade, forms the network nano structure of solid.Present invention also offers the preparation method of the composite, and by two one-step hydrothermals, heat treatment at high temperature obtains the composite with 3 D stereo network nano structure.When the obtained composite of the present invention is as Anode of lithium cell material, battery energy density reaches 650 800mAh/g, and circulating battery reaches 1500 times.
Description
Technical field
The present invention relates to a kind of field of lithium, more particularly to a kind of composite of Anode of lithium cell and its preparation side
Method.
Background technology
Lithium ion battery has witnessed modern booming electronic technology, turns into modern ubiquitous portable electronic and sets
Standby essential part.However, with more and more demands with high-energy and powerful sophisticated equipment, especially mix
The development of power electric automobile is closed, the performance of commercial Li-ion battery has been difficult to reach the performance needed for it.It is wherein important
A reason be because the current anode main material of lithium ion battery be graphite, its theoretical capacity only has 372mAh/g, its
Lithium storage content is high not enough, and the lithium ion battery for being not met by future must be to the demand that high power capacity direction is developed；And
During battery works, Li dendrite is likely to be formed in graphite surface, easily induces safety problem.Therefore, it is extensive to study always
It is directed to seeking effective method to realize more preferable anode material.
With graphite-phase ratio, transition metal oxide is that have high power capacity and relatively high operating voltage and graphite-phase ratio, separately
The outer formation problem that can also avoid using Li dendrite caused by graphite.However, in embedding, the de- cyclic process of lithium, transition gold
There is serious volumetric expansion and contraction in category oxide anode material, the destruction of material structure and mechanical efflorescence are caused, so as to lead
Send a telegraph the decline of pole cycle performance.If it is research class important in lithium electricity to solve this problem and improve the capacity of lithium battery
Topic.
The content of the invention
The problem of present invention exists for the actual demand of lithium ion battery development and prior art, offer one kind is provided and is used as
Composite of Anode of lithium cell and preparation method thereof.
The invention provides a kind of composite for Anode of lithium cell and preparation method thereof, by cupric oxide, W2O3And C
Three is compounded to form, and cupric oxide is equably arranged in opper matrix of sufficient porosity surface, the piece of cupric oxide nano blade in three dimendional blade shape
Thickness about 20-35nm, W2O3The surface of cupric oxide is coated on C, on the basis of the three-dimensional architecture of cupric oxide nano blade, is formed
Three-dimensional network nano structure.
Present invention also offers the preparation method for preparing the above-mentioned composite as Anode of lithium cell, specific steps are such as
Under：
(1) Porous Cu is immersed in 1M KOH solution, is subsequently placed in 160 DEG C of baking 3-5 hours, Zhi Houqu in baking oven
Go out to carry out the cleaning repeatedly of deionized water, then the Porous Cu is immersed to 1M dilute hydrochloric acid solution 10-20 minutes, taking out afterwards should
Porous Cu, boiler tube is placed in, under atmospheric environment, after 450-550 DEG C is annealed -1 hour 30 minutes, natural cooling, now obtained
The Porous Cu of superficial growth cupric oxide；
(2) by 0.4g-0.5g W (NO3)3And 0.2g glucose is mixed and is dissolved in 40ml deionized water and forms water
Solution, the Porous Cu of superficial growth cupric oxide made from step 1) is placed in the aqueous solution, is placed in autoclave, is heated to
200-250 DEG C and 3-5 hours are incubated, take out afterwards, after being cleaned repeatedly with deionized water and ethanol, be placed in baking oven 70-80 DEG C
12-20 hours are dried, are placed in afterwards in boiler tube, are passed through the nitrogen for carrying a small amount of hydrogen, after 600 DEG C of -700 DEG C of annealing 1-2 hours,
Naturally cool to room temperature.
Further, ammonia purity is 99.9% during annealing process procedure in step 2), flow 100sccm.
The beneficial effects of the present invention are：The three-dimensional architecture that cupric oxide nano blade is built, to eventually form mesh nano
The composite of structure provides a support, and the three-dimensional network structure eventually formed is very beneficial for alleviating and absorbs oxidation
The inner tensions that molybdenum Volume Changes in cyclic process are brought, so as to the electrode cycle performance of lifting.In addition, using Porous Cu as base
Body so that in follow-up lithium battery preparation process, directly using the matrix as collector, eliminate the step of collector makes.
Brief description of the drawings
Fig. 1 is the SEM figures of the cupric oxide of Porous Cu superficial growth in the step 1) of embodiment 1.
Fig. 2 is the SEM figures for the composite that embodiment 1 is finally prepared.
Embodiment
The present invention is further illustrated below in conjunction with drawings and the specific embodiments.
Embodiment 1
(1) Porous Cu is immersed in 1M KOH solution, is subsequently placed in baking oven 160 DEG C and toasts 3 hours, take out afterwards
The cleaning repeatedly of deionized water is carried out, then the Porous Cu is immersed to 1M dilute hydrochloric acid solution 15 minutes, it is porous to take out this afterwards
Copper, boiler tube is placed in, under atmospheric environment, after 500 DEG C are annealed 45 minutes, natural cooling, now obtains superficial growth cupric oxide
Porous Cu；
(2) by 0.4g W (NO3)3And 0.2g glucose is mixed and is dissolved in 40ml deionized water and forms the aqueous solution,
The Porous Cu of superficial growth cupric oxide made from step 1) is placed in the aqueous solution, is placed in autoclave, is heated to 250 DEG C simultaneously
Insulation 3 hours, takes out afterwards, after being cleaned repeatedly with deionized water and ethanol, is placed in baking oven 80 DEG C of dryings 12 hours, it is rearmounted
In boiler tube, the nitrogen for carrying a small amount of hydrogen is passed through, after 700 DEG C are annealed 1 hour, naturally cools to room temperature, wherein ammonia purity
For 99.9%, flow 100sccm.
Embodiment 2
(1) Porous Cu is immersed in 1M KOH solution, is subsequently placed in baking oven 160 DEG C and toasts 5 hours, take out afterwards
The cleaning repeatedly of deionized water is carried out, then the Porous Cu is immersed to 1M dilute hydrochloric acid solution 10 minutes, it is porous to take out this afterwards
Copper, boiler tube is placed in, under atmospheric environment, after 550 DEG C are annealed 30 minutes, natural cooling, now obtains superficial growth cupric oxide
Porous Cu；
(2) by 0.6g W (NO3)3And 0.2g glucose is mixed and is dissolved in 40ml deionized water and forms the aqueous solution,
The Porous Cu of superficial growth cupric oxide made from step 1) is placed in the aqueous solution, is placed in autoclave, is heated to 200 DEG C simultaneously
Insulation 5 hours, takes out afterwards, after being cleaned repeatedly with deionized water and ethanol, is placed in baking oven 70 DEG C of dryings 20 hours, it is rearmounted
In boiler tube, the nitrogen for carrying a small amount of hydrogen is passed through, after 600 DEG C are annealed 2 hours, naturally cools to room temperature, wherein ammonia purity
For 99.9%, flow 100sccm.
Embodiment 3
(1) Porous Cu is immersed in 1M KOH solution, is subsequently placed in baking oven 160 DEG C and toasts 4 hours, take out afterwards
The cleaning repeatedly of deionized water is carried out, then the Porous Cu is immersed to 1M dilute hydrochloric acid solution 20 minutes, it is porous to take out this afterwards
Copper, boiler tube is placed in, under atmospheric environment, after 450 DEG C are annealed 1 hour, natural cooling, now obtains superficial growth cupric oxide
Porous Cu；
(2) by 0.45g W (NO3)3And 0.2g glucose is mixed and is dissolved in 40ml deionized water and forms the aqueous solution,
The Porous Cu of superficial growth cupric oxide made from step 1) is placed in the aqueous solution, is placed in autoclave, is heated to 200 DEG C simultaneously
Insulation 4 hours, takes out afterwards, after being cleaned repeatedly with deionized water and ethanol, is placed in baking oven 80 DEG C of dryings 17 hours, it is rearmounted
In boiler tube, the nitrogen for carrying a small amount of hydrogen is passed through, after 700 DEG C are annealed 1.5 hours, naturally cools to room temperature, wherein ammonia is pure
Spend for 99.9%, flow 100sccm.
Composite made from embodiments above is observed by ESEM (SEM), if Fig. 1 is embodiment 1
In step 1) cupric oxide of Porous Cu superficial growth SEM figure, from the figure, it can be seen that cupric oxide in three dimendional blade shape equably
Opper matrix of sufficient porosity surface, the piece thickness about 20-35nm of cupric oxide nano blade are arranged in, nano level thickness can shorten lithium electricity
The diffusion path of lithium ion when pond works.In addition, the three-dimensional nanostructured of cupric oxide, is follow-up W2O3With shapes of the C on its surface
Into framework is provided, Fig. 2 is the SEM figures that embodiment 1 finally obtains composite, from the figure, it can be seen that W2O3Oxygen is coated on C
Change the surface of copper, on the basis of the three-dimensional architecture that cupric oxide nano blade is built, form a three-dimensional network nano structure.
Three-dimensional network structure is very beneficial for alleviating and absorbed the inner tensions that molybdenum oxide Volume Changes in cyclic process are brought, from
And the electrode cycle performance lifted.
It is Anode of lithium cell material by composite material preforms made from each embodiment, button is made using lithium metal as to electrode
Battery, carry out discharge and recharge and loop test, the charging and discharging curve under 300mA/g current density.Because the present invention is with porous
Copper is matrix so that in follow-up lithium battery preparation process, directly using the matrix as collector, eliminates collector making
Step.
Test result shows battery energy density in 650-800mAh/g.Battery capacity decays to the 80% of rated capacity
When, the circulating battery number undergone reaches 1500 times；Such as the specific data that following table one is each embodiment electrical performance testing.
Obviously, embodiments described above is only part of the embodiment of the present invention, rather than whole embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art obtained under the premise of creative work is not made it is all its
His embodiment, belongs to the scope of protection of the invention.
Each embodiment electrical performance testing data of table one
Claims (3)
- A kind of 1. composite for Anode of lithium cell and preparation method thereof, it is characterised in that：The composite is by aoxidizing Copper, W2O3It is compounded to form with C three, wherein cupric oxide is equably arranged in opper matrix of sufficient porosity surface, cupric oxide in three dimendional blade shape Piece the thickness about 20-35nm, W of blade2O3The surface of cupric oxide nano blade is coated on C, in the three-dimensional of cupric oxide nano blade On the basis of framework, the composite forms the network nano structure of solid.
- A kind of 2. composite for Anode of lithium cell according to claim 1 and preparation method thereof, it is characterised in that It is as follows including step：1) Porous Cu is immersed in 1M KOH solution, is subsequently placed in 160 DEG C of baking 3-5 hours in baking oven, taken out carry out afterwards The cleaning repeatedly of deionized water, then the Porous Cu is immersed to 1M dilute hydrochloric acid solution 10-20 minutes, it is porous to take out this afterwards Copper, boiler tube is placed in, under atmospheric environment, after 450-550 DEG C is annealed -1 hour 30 minutes, natural cooling, now obtains surface Grow the Porous Cu of cupric oxide；2) by 0.4g-0.5g W (NO3)3And 0.2g glucose is mixed and is dissolved in 40ml deionized water and forms the aqueous solution, The Porous Cu of superficial growth cupric oxide made from step 1) is placed in the aqueous solution, is placed in autoclave, is heated to 200-250 DEG C and be incubated 3-5 hours, take out afterwards, after being cleaned repeatedly with deionized water and ethanol, be placed in 70-80 DEG C of dry 12- in baking oven 20 hours, it is placed in afterwards in boiler tube, is passed through ammonia, after 600 DEG C of -700 DEG C of annealing 1-2 hours, naturally cools to room temperature.
- A kind of 3. composite for Anode of lithium cell according to claim 2 and preparation method thereof, it is characterised in that： Ammonia purity is 99.9% in annealing process procedure in step 2), flow 100sccm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120034523A1 (en) * | 2010-08-06 | 2012-02-09 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery and rechargeable lithium battery including same |
| CN105932295A (en) * | 2016-04-22 | 2016-09-07 | 清华大学深圳研究生院 | Metal lithium secondary battery and negative electrode and porous copper current collector thereof |
| CN106558692A (en) * | 2015-09-30 | 2017-04-05 | 中国科学院大连化学物理研究所 | A kind of lithium battery negative pole and its preparation and application |
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2017
- 2017-08-25 CN CN201710747681.1A patent/CN107492650B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120034523A1 (en) * | 2010-08-06 | 2012-02-09 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery and rechargeable lithium battery including same |
| CN106558692A (en) * | 2015-09-30 | 2017-04-05 | 中国科学院大连化学物理研究所 | A kind of lithium battery negative pole and its preparation and application |
| CN105932295A (en) * | 2016-04-22 | 2016-09-07 | 清华大学深圳研究生院 | Metal lithium secondary battery and negative electrode and porous copper current collector thereof |
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