CN107785547A - A kind of preparation method of carbon nitrogen iron composite negative pole material - Google Patents
A kind of preparation method of carbon nitrogen iron composite negative pole material Download PDFInfo
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- CN107785547A CN107785547A CN201710850387.3A CN201710850387A CN107785547A CN 107785547 A CN107785547 A CN 107785547A CN 201710850387 A CN201710850387 A CN 201710850387A CN 107785547 A CN107785547 A CN 107785547A
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- iron
- negative pole
- composite negative
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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
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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
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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
- H01M4/58—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
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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
Abstract
The invention discloses a kind of preparation method of carbon nitrogen iron composite negative pole material, methods described is prepared for the carbon growth in situ Fe of N doping by a step pyrolysismethod3N, method is simple, and structure is novel, and excellent storage sodium performance is showed by the product prepared by the method；Hard carbon composition is used for negative material carbon coating agent by the present invention, and negative material specific capacity is high, and cycle performance and high rate performance are excellent.
Description
Technical field
The present invention relates to battery material field, and in particular to a kind of preparation method of carbon nitrogen iron composite negative pole material.
Background technology
With global energy crisis problem getting worse, it is current science and technology to develop cleanliness without any pollution and renewable novel energy
The important directions of research.And lithium ion battery is because with energy density is high, voltage is steady, it is small with self-discharge rate to have extended cycle life
The advantages that operating temperature range is wide, safe memory-less effect is increasingly subject to the attention of people.
Due to Na elements in nature rich reserves, account for 2.64% and widely distributed, development cost of earth's crust reserves
It is cheap.Compared with lithium rechargeable battery, sodium-ion battery (SIB) has the characteristics that cost is low, safe, it is considered to be non-
Often there is the secondary cell system of development potentiality.At present, the relatively advanced country of some battery technologies is electric by sodium ion in the world
Pool technology is classified as an important basic and perspective study field, and the energy-storage battery technology hair paid close attention to as future
Open up direction.Try to explore specific capacity height, have extended cycle life, have a safety feature, the new sodium-ion battery that temperature applicable range is wide
Negative material system, have become the common problem for researching and developing high-performance sodium ion secondary battery electrode material in the world.
Anode material of lithium-ion battery main research includes tin-based material, oxide, alloy material, sulfide and phosphorus
Compound etc..Nitride (the Fe of iron2N,Fe3N) have that stability is high, low cost, wide material sources, it is nontoxic the advantages that, with existing stone
Electrode ink (372mAhg-1) compare, there is significant advantage.
Hard charcoal is that a kind of be crosslinked by graphite microcrystal with impalpable structure accumulates the novel anode material formed, the layer of the material
Spacing, more than the 0.34nm of graphite, is advantageous to the quick of sodium ion and is embedded in abjection, and material exists between 0.38-0.4nm
Deformational stress is smaller during the deintercalation repeatedly of sodium ion, is capable of the stability of holding structure, and these performances are final in the battery
It is presented as the quickening of charging rate and the extension of service life.
The content of the invention
The present invention provides a kind of preparation method of carbon nitrogen iron composite negative pole material, and methods described is prepared by a step pyrolysismethod
The carbon growth in situ Fe of N doping3N, method is simple, and structure is novel, is showed by the product prepared by the method excellent
Store up sodium performance；Hard carbon composition is used for negative material carbon coating agent by the present invention, and negative material specific capacity is high, cycle performance and multiplying power
Function admirable.
To achieve these goals, the present invention provides a kind of preparation method of carbon nitrogen iron composite negative pole material, this method bag
Include following steps：
（1）Prepare nitrided iron
It is 40 in mass ratio by urea and ironic citrate:(15-35) is dissolved in deionized water, is stirred, and is then freezed
It is dried to obtain product one；
Product one is pyrolyzed, obtains product two, is pyrolyzed and is carried out in vacuum tube furnace, helium is to protect gas, pyrolysis temperature
For 600-700 DEG C, reaction time 3-5h；
Product two is washed with deionized water and acetone, obtains nitrided iron；
（2）Weigh starch to be dissolved in absolute ethyl alcohol, stir 5-6h, form uniform solution, above-mentioned nitridation is then added into solution
Iron and and crosslinking agent, 10-18h is crosslinked under the conditions of 120-180 DEG C, obtains solid precursor；Wherein starch, nitrided iron, nothing
The mass ratio of water-ethanol and crosslinking agent is 1：（15-20）：（30-45）：（0.5-0.7）；
（3）Solid precursor is crushed and sieved, obtains the hard charcoal coated powder presoma that particle diameter is 10-20 μm；
Under the inert gas shielding of circulation, hard charcoal coated powder presoma is fitted into tube furnace, and with 5-8 DEG C/min liter
Warm speed is heated to 450-580 DEG C, is incubated 3-5h, is carbonized in advance；
After pre- carbonisation terminates, then the temperature of tube furnace is risen to 1000-1200 DEG C with 10-15 DEG C/min programming rate and incited somebody to action
Material is carbonized, and obtains carbon nitrogen iron composite negative pole material.
The invention has the advantages that and remarkable result：
（1）The method of the invention is prepared for the carbon growth in situ Fe of N doping by a step pyrolysismethod3N, method is simple, structure
Novelty, excellent storage sodium performance is showed by the product prepared by the method；
（2）Hard carbon composition is used for negative material carbon coating agent by the present invention, negative material specific capacity height, cycle performance and forthright again
Can be excellent.
Embodiment
Embodiment one
It is 40 in mass ratio by urea and ironic citrate:15 are dissolved in deionized water, stir, and are then freeze-dried
To product one.
Product one is pyrolyzed, obtains product two, is pyrolyzed and is carried out in vacuum tube furnace, helium is protection gas, is pyrolyzed
Temperature is 600 DEG C, reaction time 3h；Product two is washed with deionized water and acetone, obtains nitrided iron.
Weigh starch to be dissolved in absolute ethyl alcohol, stir 5h, form uniform solution, above-mentioned nitrided iron is then added into solution
And and crosslinking agent, 10h is crosslinked under the conditions of 120 DEG C, obtains solid precursor；Wherein starch, nitrided iron, absolute ethyl alcohol and friendship
The mass ratio for joining agent is 1：15：30：0.5.
Solid precursor is crushed and sieved, obtains the hard charcoal coated powder presoma that particle diameter is 10-20 μm；Flowing
Under logical inert gas shielding, hard charcoal coated powder presoma is fitted into tube furnace, and heated with 5 DEG C/min programming rate
To 450 DEG C, 3h is incubated, is carbonized in advance；After pre- carbonisation terminates, then with 10 DEG C/min programming rate by the temperature of tube furnace
Degree rises to 1000 DEG C and material is carbonized, and obtains carbon nitrogen iron composite negative pole material.
Embodiment two
It is 40 in mass ratio by urea and ironic citrate:35 are dissolved in deionized water, stir, and are then freeze-dried
To product one.
Product one is pyrolyzed, obtains product two, is pyrolyzed and is carried out in vacuum tube furnace, helium is protection gas, is pyrolyzed
Temperature is 700 DEG C, reaction time 5h；Product two is washed with deionized water and acetone, obtains nitrided iron.
Weigh starch to be dissolved in absolute ethyl alcohol, stir 6h, form uniform solution, above-mentioned nitrided iron is then added into solution
And and crosslinking agent, 18h is crosslinked under the conditions of 180 DEG C, obtains solid precursor；Wherein starch, nitrided iron, absolute ethyl alcohol and friendship
The mass ratio for joining agent is 1：20：45：0.7.
Solid precursor is crushed and sieved, obtains the hard charcoal coated powder presoma that particle diameter is 10-20 μm；Flowing
Under logical inert gas shielding, hard charcoal coated powder presoma is fitted into tube furnace, and is added with 5-8 DEG C/min programming rate
Heat is incubated 5h, is carbonized in advance to 580 DEG C；After pre- carbonisation terminates, then with 15 DEG C/min programming rate by tube furnace
Temperature rises to 1200 DEG C and material is carbonized, and obtains carbon nitrogen iron composite negative pole material.
Sodium-ion battery negative plate, metallic sodium piece, electrolyte made from above-described embodiment one, two products therefroms are assembled into
Sodium-ion battery, for carrying out constant current charge-discharge test, in 100mAg-1Current density under, discharge capacity is respectively first
394mAh/g and 386mAh/g, capacity is 315mAh/g and 306mAh/g after circulating 50 times, has good cyclical stability.
Claims (1)
1. a kind of preparation method of carbon nitrogen iron composite negative pole material, this method comprise the following steps：
（1）Prepare nitrided iron
It is 40 in mass ratio by urea and ironic citrate:(15-35) is dissolved in deionized water, is stirred, and is then freezed
It is dried to obtain product one；
Product one is pyrolyzed, obtains product two, is pyrolyzed and is carried out in vacuum tube furnace, helium is to protect gas, pyrolysis temperature
For 600-700 DEG C, reaction time 3-5h；
Product two is washed with deionized water and acetone, obtains nitrided iron；
（2）Weigh starch to be dissolved in absolute ethyl alcohol, stir 5-6h, form uniform solution, above-mentioned nitridation is then added into solution
Iron and and crosslinking agent, 10-18h is crosslinked under the conditions of 120-180 DEG C, obtains solid precursor；Wherein starch, nitrided iron, nothing
The mass ratio of water-ethanol and crosslinking agent is 1：（15-20）：（30-45）：（0.5-0.7）；
（3）Solid precursor is crushed and sieved, obtains the hard charcoal coated powder presoma that particle diameter is 10-20 μm；
Under the inert gas shielding of circulation, hard charcoal coated powder presoma is fitted into tube furnace, and with 5-8 DEG C/min liter
Warm speed is heated to 450-580 DEG C, is incubated 3-5h, is carbonized in advance；
After pre- carbonisation terminates, then the temperature of tube furnace is risen to 1000-1200 DEG C with 10-15 DEG C/min programming rate and incited somebody to action
Material is carbonized, and obtains carbon nitrogen iron composite negative pole material.
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| CN201710850387.3A CN107785547A (en) | 2017-09-15 | 2017-09-15 | A kind of preparation method of carbon nitrogen iron composite negative pole material |
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| CN201710850387.3A CN107785547A (en) | 2017-09-15 | 2017-09-15 | A kind of preparation method of carbon nitrogen iron composite negative pole material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109305684A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | Carbon-encapsulated iron and cementite nanocomposite and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106981629A (en) * | 2016-01-16 | 2017-07-25 | 山东玉皇新能源科技有限公司 | A kind of preparation of lithium-ion-power cell hard carbon cathode material and its method of modifying |
| CN107068994A (en) * | 2017-01-17 | 2017-08-18 | 陕西科技大学 | A kind of preparation method of the carbon load nitridation iron complexes anode material of lithium-ion battery of N doping |
-
2017
- 2017-09-15 CN CN201710850387.3A patent/CN107785547A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106981629A (en) * | 2016-01-16 | 2017-07-25 | 山东玉皇新能源科技有限公司 | A kind of preparation of lithium-ion-power cell hard carbon cathode material and its method of modifying |
| CN107068994A (en) * | 2017-01-17 | 2017-08-18 | 陕西科技大学 | A kind of preparation method of the carbon load nitridation iron complexes anode material of lithium-ion battery of N doping |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109305684A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | Carbon-encapsulated iron and cementite nanocomposite and preparation method thereof |
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