CN110148753A - A kind of Magnesium ion battery baseband processing method and Magnesium ion battery - Google Patents
A kind of Magnesium ion battery baseband processing method and Magnesium ion battery Download PDFInfo
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- CN110148753A CN110148753A CN201910428427.4A CN201910428427A CN110148753A CN 110148753 A CN110148753 A CN 110148753A CN 201910428427 A CN201910428427 A CN 201910428427A CN 110148753 A CN110148753 A CN 110148753A
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- ion battery
- magnesium ion
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
-
- 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
- H01M4/58—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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/808—Foamed, spongy materials
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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 invention belongs to electrochemical technology field, a kind of Magnesium ion battery baseband processing method and Magnesium ion battery are disclosed.The processing method is the following steps are included: be made gel for the mixing of carbon source, thickener and water, then even application is on sponge；Then will treated that sponge is attached on aluminium foil, cracked under high temperature, generate three-dimensional network electric conductor on aluminium foil to get treated Magnesium ion battery base band.The present invention is matrix using sponge, and three-dimensional network collector is made, and makes the particle of positive active material that can touch conductive network, improves electric conductivity；By gained treated Magnesium ion battery base band is fabricated to battery, it is 85~91% that 20C, which puts a capacity relative to the ratio of 1C capacity, hence it is evident that higher than the Magnesium ion battery of Magnesium ion battery base band preparation that is without any processing and generating by cracking acetylene carbon-coating.
Description
Technical field
The invention belongs to electrochemical technology field, in particular to a kind of Magnesium ion battery baseband processing method and magnesium ion electricity
Pond.
Background technique
With economic and science and technology continuous development, demand of the mankind to the energy increasingly increases.Fossil energy faces withered at present
Exhaust, people increase the dynamics for developing various renewable energy, solar energy, wind energy etc. start energy field occupy a seat it
Ground.However these renewable energy are affected by weather and time, have apparent unstability, discontinuity and uncontrollable
Property, need to develop special apparatus for storing electrical energy to guarantee the stability of power generation, power supply.Existing energy storage device
In, can fill energy-storage battery is most common energy storage device, and the lithium ion battery with high-energy density and cycle performance, is in recent years
Come the hot spot studied and applied, still, global lithium resource is not rich, is used for power electric as lithium ion battery is more and more
Pond, lithium resource also face exhaustion as fossil energy.
Magnesium ion battery is considered as the new secondary battery of great potential, magnesium reserves very abundant on earth, China
Magnesium resource reserves occupy first place in the world, the price of magnesium is more much lower than lithium, with magnesium substitution lithium exploitation magnesium ion energy-storage battery have it is non-
Often wide application prospect.Already just there is the research of Magnesium ion battery to report in last century the seventies, but Magnesium ion battery
Commercial kitchen area slowly is not entered into, one of the main reasons is positive electrode poorly conductive itself, and performance cannot be brought into play completely.
Traditional method are as follows: in one layer of carbon of Surface Creation of base band, improve the electric conductivity of pole piece, led although this method can improve
Limited extent that is electrical, but improving.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that providing a kind of magnesium ion electricity
Pond baseband processing method.
Another object of the present invention is to provide the Magnesium ion battery base band of above method preparation.
Still a further object of the present invention is to provide a kind of anode of magnesium ion battery material.
Still a further object of the present invention is to provide a kind of Magnesium ion battery.
The purpose of the present invention is realized by following proposal:
A kind of Magnesium ion battery baseband processing method comprising following steps:
(1) gel is made in the mixing of carbon source, thickener and water, then even application is on sponge；
(2) by treated in step (1), sponge is attached on aluminium foil, cracks under high temperature, three-dimensional network is generated on aluminium foil
Electric conductor is to get treated Magnesium ion battery base band.
Carbon source described in step (1) is at least one of glucose, pitch, sucrose；Carbon source cracks life at high temperature
At carbon, carbon plays electric action.
Thickener described in step (1) is thickener commonly used in the art, preferably PVA (polyvinyl alcohol), CMC
At least one of (sodium carboxymethylcellulose), HPMC (hydroxypropyl methyl cellulose)；Thickener primarily serves the effect of gel.
The dosage of carbon source, thickener and water described in step (1) meet carbon source, thickener and water mass ratio be 5~
30:2:50；
Sponge described in step (1) with a thickness of 0.5~2mm；Carbon source described in step (1), thickener and water
It is 1:1 that the dosage of gel mixture and sponge, which meets gel mixture and the weight ratio of sponge,；Due to the viscosity of gel mixture
It is very low, therefore the thickness of the three-dimensional network electric conductor of step (2) formation and sponge thickness are almost the same.
Pintsch process described in step (2) refers in 650-800 DEG C of cracking 3-8h, preferably 650 DEG C cracking 4h；
A kind of anode of magnesium ion battery base band prepared by the above method.
A kind of anode of magnesium ion battery piece comprising above-mentioned anode of magnesium ion battery base band and positive electrode, wherein just
Pole material includes positive electrode active materials, conductive carbon, PVDF and NMP, wherein the matter of positive electrode active materials, conductive carbon, PVDF and NMP
Amount is than being 100:3:5:110；The positive electrode active materials are preferably magnesium sulfide.
A kind of Magnesium ion battery comprising above-mentioned anode of magnesium ion battery piece.
Preferably, the negative electrode tab of above-mentioned Magnesium ion battery is magnesium metal, and diaphragm PE, electrolyte is 0.25mol/L's
Mg(AlCl2BuEt)2/THF。
Mechanism of the invention are as follows:
The present invention is matrix using sponge, to its surface spraying carbon source, the gel mixture of thickener and water, due to gel
The viscosity of mixture is lower, and when gel mixture is sprayed on sponge surface, gel mixture can penetrate into the interior of sponge
Portion, i.e., not only six surfaces of sponge are even all impregnated with gel mixture inside it, after high-temperature calcination, the every silk of sponge
On all uniformly cladding one layer of carbon, formed three-dimensional network collector.Sponge is identical as the area for the side that positive plate contacts with each other,
Therefore the particle of positive active material can touch conductive network, improve electric conductivity.
The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that
The present invention generates one layer of netted conductive network base band in base band, increases substantially conductive effect.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Agents useful for same can routinely be bought unless otherwise specified from market in embodiment.Sponge used and aluminium foil in embodiment
Size meet the side area equation to contact with each other of sponge and aluminium foil；
Embodiment 1
By glucose, PVA, water, 5:2:50 is mixed in proportion, and stirring is made gel, even application to etc. quality it is rectangular
On the sponge of body, sponge is attached on aluminium foil, is cracked under high temperature, the temperature of cracking is at 650 degree, the duration 4 hours, in aluminium foil
Upper generation with a thickness of 1mm three-dimensional network electric conductor to get treated Magnesium ion battery base band.
Embodiment 2
By glucose, PVA, water, 10:2:50 is mixed in proportion, and stirring is made gel, even application to etc. quality it is rectangular
On the sponge of body, sponge is attached on aluminium foil, is cracked under high temperature, the temperature of cracking at 650 degree or so, the duration about 4 hours,
The three-dimensional network electric conductor with a thickness of 1mm is generated on aluminium foil to get treated Magnesium ion battery base band.
Embodiment 3
By glucose, PVA, water, 20:2:50 is mixed in proportion, and stirring is made gel, even application to etc. quality it is rectangular
On the sponge of body, sponge is attached on aluminium foil, is cracked under high temperature, the temperature of cracking is at 650 degree, the duration 4 hours, in aluminium foil
Upper generation with a thickness of 1mm three-dimensional network electric conductor to get treated Magnesium ion battery base band.
Embodiment 4
By glucose, PVA, water, 30:2:50 is mixed in proportion, and stirring is made gel, even application to etc. quality it is rectangular
On the sponge of body, sponge is attached on aluminium foil, is cracked under high temperature, the temperature of cracking is at 650 degree, the duration 4 hours, in aluminium foil
Upper generation with a thickness of 1mm three-dimensional network electric conductor to get treated Magnesium ion battery base band.
Embodiment 5
By pitch, PVA, water, 5:2:50 is mixed in proportion, and stirring is made gel, even application to etc. quality cuboid
Sponge on, sponge is attached on aluminium foil, is cracked under high temperature, the temperature of cracking is at 650 degree, the duration 4 hours, on aluminium foil
The three-dimensional network electric conductor with a thickness of 1mm is generated to get treated Magnesium ion battery base band.
Embodiment 6
By glucose, CMC, water, 5:2:50 is mixed in proportion, and stirring is made gel, even application to etc. quality it is rectangular
On the sponge of body, sponge is attached on aluminium foil, is cracked under high temperature, the temperature of cracking is at 650 degree, the duration 4 hours, in aluminium foil
Upper generation with a thickness of 1mm three-dimensional network electric conductor to get treated Magnesium ion battery base band.
Comparing embodiment 1
Aluminium foil does not take any treatment measures
Comparing embodiment 2
Aluminium foil is used into conventional method, acetylene gas is passed through at high temperature and is cracked, generates a thickness in aluminium foil surface
Degree is 1mm conductive carbon, cracking condition: 650-800 DEG C of cracking 3-8h.
Battery base band prepared by above embodiments and comparative example is fabricated to battery, specific steps are as follows: by magnesium sulfide:
Graphite: PVDF, NMP are mixed by 100:3:5:110 (mass ratio), are coated to aluminium foil (the i.e. Examples 1 to 6 of the above processing
With treated the Magnesium ion battery base band of comparative example 1~2) on, it being negative pole piece with metal magnesium rod, PE film is diaphragm, with
Mg (the AlCl of 0.25mol/L2BuEt)2/ THF is electrolyte, is assembled into 18650 type batteries in the glove box full of argon gas.
The discharge capacity of above-mentioned 18650 type battery 1C and 20C are tested, the results are shown in Table 1:
The discharge capacity of the 20C and 1C of the battery of the battery base band of 1 Examples 1 to 6 of table and comparative example 1 preparation
| 20C discharge capacity (opposite 1C discharge capacity) | |
| Embodiment 1 | 85% |
| Embodiment 2 | 89% |
| Embodiment 3 | 91% |
| Embodiment 4 | 91% |
| Embodiment 5 | 85% |
| Embodiment 6 | 85% |
| Comparing embodiment 1 | 62% |
| Comparing embodiment 2 | 73% |
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of Magnesium ion battery baseband processing method, it is characterised in that the following steps are included:
(1) gel is made in the mixing of carbon source, thickener and water, then even application is on sponge；
(2) by treated in step (1), sponge is attached on aluminium foil, is cracked under high temperature, and it is conductive that three-dimensional network is generated on aluminium foil
Body is to get treated Magnesium ion battery base band.
2. Magnesium ion battery baseband processing method according to claim 1, it is characterised in that:
Carbon source described in step (1) is at least one of glucose, pitch, sucrose；
Thickener described in step (1) is at least one of PVA, CMC, HPMC.
3. Magnesium ion battery baseband processing method according to claim 1, it is characterised in that:
The mass ratio that the dosage of carbon source, thickener and water described in step (1) meets carbon source, thickener and water is 5~30:2:
50。
4. Magnesium ion battery baseband processing method according to claim 1, it is characterised in that:
Sponge described in step (1) with a thickness of 0.5~2mm；The gel of carbon source described in step (1), thickener and water
It is 1:1 that the dosage of mixture and sponge, which meets gel mixture and the weight ratio of sponge,.
5. Magnesium ion battery baseband processing method according to claim 1, it is characterised in that:
Pintsch process described in step (2) refers in 650-800 DEG C of cracking 3-8h.
6. a kind of magnesium ion that Magnesium ion battery baseband processing methods described in any item according to claim 1~5 are handled
Anode base band.
7. a kind of anode of magnesium ion battery piece, it is characterised in that including anode of magnesium ion battery base band as claimed in claim 6 and
Positive electrode, the positive electrode include positive electrode active materials, conductive carbon, PVDF and NMP.
8. anode of magnesium ion battery piece according to claim 7, it is characterised in that:
Positive electrode active materials in the positive electrode, conductive carbon, PVDF and NMP mass ratio be 100:3:5:110；Described
Positive electrode active materials are magnesium sulfide.
9. a kind of Magnesium ion battery, it is characterised in that including anode of magnesium ion battery piece described in claim 7 or 8.
10. Magnesium ion battery according to claim 9, it is characterised in that:
The negative electrode tab of the Magnesium ion battery is magnesium metal, and diaphragm PE, electrolyte is the Mg of 0.25mol/L
(AlCl2BuEt)2/THF。
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| CN201910428427.4A CN110148753A (en) | 2019-05-22 | 2019-05-22 | A kind of Magnesium ion battery baseband processing method and Magnesium ion battery |
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| CN201910428427.4A CN110148753A (en) | 2019-05-22 | 2019-05-22 | A kind of Magnesium ion battery baseband processing method and Magnesium ion battery |
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| CN106981631A (en) * | 2017-03-22 | 2017-07-25 | 陕西科技大学 | A kind of nitrogen-doped carbon micro Nano material and its preparation method and application |
| CN107342172A (en) * | 2016-12-23 | 2017-11-10 | 辽宁卓异新材料有限公司 | A kind of three-dimensional networkses structure electrode material and preparation method thereof |
| CN109052359A (en) * | 2018-08-06 | 2018-12-21 | 中国科学技术大学 | Three-dimensional carbon material and preparation method thereof, lithium metal combination electrode and preparation method thereof |
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2019
- 2019-05-22 CN CN201910428427.4A patent/CN110148753A/en active Pending
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|---|---|---|---|---|
| CN101800311A (en) * | 2010-02-08 | 2010-08-11 | 北京理工大学 | Method for preparing lithium iron phosphate with high rate discharge by using ultrasonic coprecipitation |
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Application publication date: 20190820 |