CN101834287A - Preparation method of anode material of lithium ion battery - Google Patents
Preparation method of anode material of lithium ion battery Download PDFInfo
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- CN101834287A CN101834287A CN200910037820A CN200910037820A CN101834287A CN 101834287 A CN101834287 A CN 101834287A CN 200910037820 A CN200910037820 A CN 200910037820A CN 200910037820 A CN200910037820 A CN 200910037820A CN 101834287 A CN101834287 A CN 101834287A
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- lifepo
- nano silver
- preparation
- lithium
- anode material
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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 relates to a preparation method of an anode material of a lithium ion battery, which comprises the following process steps of: mixing a trivalent iron source, a lithium source and a phosphorus source according to a stoichiometric ratio of LiFePO4; adding a proper amount of reducing agent into the mixture; preparing a LiFePO4 material by a carbothermic method; and adding silver nanoparticles prepared by a liquid phase chemical reduction method into the LiFePO4 material to obtain a nano-silver coated LiFePO4 product through a high-energy ball milling process. The nano-silver coated LiFePO4 anode material prepared by the method has fine particles and high electrical conductivity, and has a great application value in the field of dynamic lithium ion batteries.
Description
One, technical field
The present invention relates to a kind of method for preparing anode material of lithium-ion battery, belong to energy and material and technical field of new material preparation.
Two, technical background
Lithium ion battery is the with fastest developing speed also the most valued present novel high-energy storage battery, as the first-selected object that can fill the formula power supply again, lithium ion battery not only is widely used in portable type electronic products such as mobile phone, notebook computer, video camera, digital camera, also has broad application prospects in each fields such as energy storage, communication, space flight.But at present lithium ion battery is based on low capacity, low-power, for reducing an urgent demand of the use electric automobile that environmental pollution proposes, is badly in need of the big capacity of exploitation, high power, high security lithium ion battery cheaply.
Positive electrode is the important component part of lithium ion battery.Business-like LiCoO
2And derivative rely on synthetic simple, capacity is higher, discharge and recharge advantage such as more steady still in occupation of small-scale lithium ion cell market, but cobalt resource shortage, price be higher, severe toxicity is arranged, the material thermal stability is relatively poor, exist safety problem, and these problems all make cobalt acid lithium material be difficult to become the selection of large-scale anode material of lithium battery.And be in LiNiO in the experimental study always
2Except having potential safety hazard, shortcoming such as it also has synthetic difficulty, side reaction is arranged when storing, discharge potential is lower.LiMn
2O
4Although good slightly than the two aspect security performance, because its capacity attenuation in charge and discharge process is very fast, especially under hot conditions, this shortcoming makes it be used for large-scale lithium ion battery and is subjected to certain obstruction.Current society pays attention to requirements such as safety, environmental protection, LiFePO more
4Be illustrated in face of the people LiFePO with its advantageous advantage
4Have olivine structural, theoretical capacity is 170mAh/g, and discharge platform is 3.4V (vs.Li/Li
+), it has characteristics such as aboundresources, cheap, environment-protecting asepsis, excellent cycle performance, excellent security energy, is expected to become the positive electrode of big capacity, high power lithium ion cell first-selection.
Yet the LiFePO4 positive electrode has low electronic conductivity (10
-10S/cm) and Li
+Pass the shortcoming of the slow ions diffusion of two-phase interface, cause its rate capability poor.This has limited LiFePO greatly
4The application of positive electrode in practical lithium-ion.Will be with LiFePO
4Industrialization, and then be applied to powerful power-type lithium ion battery, must be to LiFePO
4Carry out modification.The research of modification direction should be devoted to improve LiFePO
4The electronic conductivity of material and ionic conductivity.
Three, summary of the invention:
At the deficiency of above technology, the object of the present invention is to provide and a kind ofly can effectively improve LiFePO
4The electronic conductivity of material and the preparation method of ionic conductivity, the product particle size of this method preparation is little, conduct electricity very well, and raw material are cheap and easy to get simultaneously, and cost is low, realizes the practical application of this material in electrokinetic cell.For realizing above-mentioned technical purpose, the present invention by the following technical solutions:
A kind of preparation method of anode material for lithium-ion batteries is characterized in that this method carries out according to the following steps: 1) with Fe
2O
3, LiOH.H
2O, NH
4H
2PO
4Press LiFePO
4The stoichiometric proportion mixing, the polyethylene of interpolation mass fraction 20%, in grinding in ball grinder 1h, calcined 10 hours under 450～700 ℃ under nitrogen protection atmosphere dry back, and cool to room temperature obtains LiFePO
4Material;
2) utilize the get everything ready nano silver particles of different-grain diameter size of liquid phase chemical reduction legal system, the nano silver particles size is at 10-80nm.
3) with step 2) make nano silver particles with 0.1%～1% ratio make LiFePO with step 1)
4Material mixing, ball milling obtained the LiFePO that Nano Silver coats in 10 hours under argon shield atmosphere
4Product.
The present invention also provides the preparation method of another anode material for lithium-ion batteries, it is characterized in that this method carries out according to the following steps:
1) LiFePO is pressed in source of iron, lithium source, phosphorus source
4The stoichiometric proportion mixing, the reducing agent of interpolation mass fraction 20%, in grinding in ball grinder 1h, calcined 10 hours under 450～700 ℃ under nitrogen protection atmosphere dry back, and cool to room temperature obtains LiFePO
4Material;
2) utilize the get everything ready nano silver particles of different-grain diameter size of liquid phase chemical reduction legal system, nano silver particles chi, very little at 10-80nm.
3) with step 2) make nano silver particles with 0.1%～1% ratio make LiFePO with step 1)
4Material mixing, ball milling obtained the LiFePO that Nano Silver coats in 10 hours under argon shield atmosphere
4Product.
Source of iron of the present invention is Fe
2O
3, Fe
3O
4Or Fe, the phosphorus source is H
3PO
4, NH
4H
2PO
4Or (NH
4)
2HPO
4Also available FePO
4Do source of iron and phosphorus source simultaneously, use LiH
2PO
4Do lithium source and phosphorus source simultaneously, reducing agent is hydrocarbons such as polyethylene.
The technology of the lithium ion anode material that the present invention set up has advantage: it is raw material that the present invention adopts cheap ferric iron source, obtains LiFePO by carbon thermal reduction
4, cost is low, adopts Nano Silver to coat LiFePO
4, good conductivity.Adopt the finished particle of ball grinding method preparation tiny, improve Li
+At LiFePO
4The ability of passing in the material makes product have good electron conduction and ionic conductivity, has very big using value in the electrokinetic cell field.
Four, embodiment:
The invention provides a kind of preparation method of anode material for lithium-ion batteries, concrete processing step is as follows: 1) LiFePO is pressed in source of iron, lithium source, phosphorus source
4The stoichiometric proportion mixing, the reducing agent of interpolation mass fraction 20%, in grinding in ball grinder 1h, calcined 10 hours under 450～700 ℃ under nitrogen protection atmosphere dry back, and cool to room temperature obtains LiFePO
4Material; 2) utilize the get everything ready nano silver particles of different-grain diameter size of liquid phase chemical reduction legal system, the nano silver particles size is at 10-80nm; 3) with step 2) make nano silver particles with 0.1%～1% ratio make LiFePO with step 1)
4Material mixing, ball milling obtained the LiFePO that Nano Silver coats in 10 hours under argon shield atmosphere
4Product.
Further understand the present invention below by several specific embodiments.
Embodiment one: press LiFePO
4Stoichiometric proportion takes by weighing raw material Fe
2O
3, LiOH.H
2O, NH
4H
2PO
4Mix; the polyethylene that adds mass fraction 20%; in grinding in ball grinder 1h (rotating speed is 450r/min); raw material behind the ball milling are taken out; put into drying box in 120 ℃ dry 12 hours down, in the following 600 ℃ of calcinings 10 hours down of nitrogen protection atmosphere, in stove, naturally cool to room temperature; in this process, continue to feed nitrogen, obtain LiFePO
4Material; Utilize the liquid phase chemical reduction legal system to be equipped with nano silver particles again, take by weighing Nano Silver and LiFePO in 1: 99 ratio
4Material stirred 30 minutes with mixer, after mixing, placed ball mill ball milling (rotating speed is 450r/min), adopted argon shield atmosphere during ball milling, after 10 hours, obtained the LiFePO that Nano Silver coats
4Product.Recording this product average grain diameter is 0.2～0.6, take by weighing this sample of 100mg, with sample powder, acetylene black and PVDF mixed with 8: 1: 1, be pressed into electrode slice, conduct is anodal after positive empty drying, make negative pole with the pure metal lithium sheet, recording this sample is 134mAh/g in room temperature with the specific discharge capacity of 1/5C constant current charge-discharge.
Embodiment two: press LiFePO
4Stoichiometric proportion takes by weighing raw material Fe
2O
3, LiOH.H
2O, NH
4H
2PO
4Mix; the polyethylene that adds mass fraction 20%; in grinding in ball grinder 1h (rotating speed is 450r/min); raw material behind the ball milling are taken out; put into drying box in 120 ℃ dry 12 hours down, in the following 700 ℃ of calcinings 10 hours down of nitrogen protection atmosphere, in stove, naturally cool to room temperature; in this process, continue to feed nitrogen, obtain LiFePO
4Material; Utilize the liquid phase chemical reduction legal system to be equipped with nano silver particles again, take by weighing Nano Silver and LiFePO in 1: 99 ratio
4Material stirred 30 minutes with mixer, after mixing, placed ball mill ball milling (rotating speed is 450r/min), adopted argon shield atmosphere during ball milling, after 10 hours, obtained the LiFePO that Nano Silver coats
4Product.Recording this product average grain diameter is 0.5～0.1, take by weighing this sample of 100mg, with sample powder, acetylene black and PVDF mixed with 8: 1: 1, be pressed into electrode slice, conduct is anodal after positive empty drying, make negative pole with the pure metal lithium sheet, recording this sample is 112mAh/g in room temperature with the specific discharge capacity of 1/5C constant current charge-discharge.。
Embodiment three: LiFePO is pressed in the method preparation identical with embodiment
4And nano-Ag particles, take by weighing Nano Silver and LiFePO in 0.5: 99.5 ratio
4Material stirred 30 minutes with mixer, after mixing, placed ball mill ball milling (rotating speed is 450r/min), adopted argon shield atmosphere during ball milling, after 10 hours, obtained the LiFePO that Nano Silver coats
4Product.Recording this product average grain diameter is 0.2～0.6, take by weighing this sample of 100mg, with sample powder, acetylene black and PVDF mixed with 8: 1: 1, be pressed into electrode slice, conduct is anodal after positive empty drying, make negative pole with the pure metal lithium sheet, recording this sample is 118mAh/g in room temperature with the specific discharge capacity of 1/5C constant current charge-discharge.
Embodiment four: LiFePO is pressed in the method preparation identical with embodiment
4And nano-Ag particles, take by weighing Nano Silver and LiFePO in 0.1: 99.9 ratio
4Material stirred 30 minutes with mixer, after mixing, placed ball mill ball milling (rotating speed is 450r/min), adopted argon shield atmosphere during ball milling, after 10 hours, obtained the LiFePO that Nano Silver coats
4Product.Recording this product average grain diameter is 0.2～0.6, take by weighing this sample of 100mg, with sample powder, acetylene black and PVDF mixed with 8: 1: 1, be pressed into electrode slice, conduct is anodal after positive empty drying, make negative pole with the pure metal lithium sheet, recording this sample is 102mAh/g in room temperature with the specific discharge capacity of 1/5C constant current charge-discharge.。
Embodiment five: LiFePO is pressed in the method preparation identical with embodiment
4And nano-Ag particles, take by weighing Nano Silver and LiFePO in 1: 99 ratio
4Material stirred 30 minutes with mixer, after mixing, placed ball mill ball milling (rotating speed is 450r/min), adopted argon shield atmosphere during ball milling, and ball milling obtained the LiFePO that Nano Silver coats after 20 hours
4Product.Recording this product average grain diameter is 0.2～0.5, take by weighing this sample of 100mg, with sample powder, acetylene black and PVDF mixed with 8: 1: 1, be pressed into electrode slice, conduct is anodal after positive empty drying, make negative pole with the pure metal lithium sheet, recording this sample is 145mAh/g in room temperature with the specific discharge capacity of 1/5C constant current charge-discharge.
Embodiment six: LiFePO is pressed in the method preparation identical with embodiment
4And nano-Ag particles, take by weighing Nano Silver and LiFePO in 1: 99 ratio
4Material stirred 30 minutes with mixer, after mixing, placed-the ball mill ball milling (rotating speed is 450r/min), adopted argon shield atmosphere during ball milling, after 30 hours, obtained the LiFePO that Nano Silver coats
4Product.Recording this product average grain diameter is 0.2～0.5, take by weighing this sample of 100mg, with sample powder, acetylene black and PVDF mixed with 8: 1: 1, be pressed into electrode slice, conduct is anodal after positive empty drying, make negative pole with the pure metal lithium sheet, recording this sample is 123mAh/g in room temperature with the specific discharge capacity of 1/5C constant current charge-discharge.
Claims (4)
1. the preparation method of an anode material for lithium-ion batteries, it is characterized in that this method clicks step and carries out: (1) is with Fe
2O
3, LiOH.H
2O, NH
4H
2PO
4Press LiFePO
4The stoichiometric proportion mixing, the polyethylene of interpolation mass fraction 20%, in grinding in ball grinder 5h, calcined 10 hours under 450～700 ℃ under nitrogen protection atmosphere dry back, and cool to room temperature obtains LiFePO
4Material; (2) utilize the get everything ready nano silver particles of different-grain diameter size of liquid phase chemical reduction legal system, the nano silver particles size is at 10-80nm; (3) with step 2) make nano silver particles with 0.1%～1% ratio make LiFePO with step 1)
4Material mixing, ball milling obtained the LiFePO that Nano Silver coats in 5 hours under argon shield atmosphere
4Product.
2. the preparation method of a kind of anode material for lithium-ion batteries according to claim 1 is characterized in that adopting polyethylene reduction preparation LiFePO
4Material.
3. the preparation method of a kind of anode material for lithium-ion batteries according to claim 1 is characterized in that LiFePO
4Material is coated with nano silver particles.
4. the preparation method of a kind of anode material for lithium-ion batteries according to claim 1 is characterized in that preparing Nano Silver by high-energy ball milling method coats LiFePO
4
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|---|---|---|---|
| CN2009100378207A CN101834287B (en) | 2009-03-11 | 2009-03-11 | Preparation method of anode material of lithium ion battery |
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|---|---|---|---|
| CN2009100378207A CN101834287B (en) | 2009-03-11 | 2009-03-11 | Preparation method of anode material of lithium ion battery |
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| Publication Number | Publication Date |
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| CN101834287A true CN101834287A (en) | 2010-09-15 |
| CN101834287B CN101834287B (en) | 2012-12-26 |
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ID=42718274
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103337627A (en) * | 2013-06-14 | 2013-10-02 | 苏州诺信创新能源有限公司 | Lithium-ion battery and lithium iron phosphate positive electrode material for same |
| CN108258212A (en) * | 2018-01-03 | 2018-07-06 | 浙江衡远新能源科技有限公司 | A kind of lithium sulfur battery anode material preparation method |
| CN108550901A (en) * | 2018-05-11 | 2018-09-18 | 美澳视界（厦门）智能科技有限公司 | A kind of high-energy high density and the graphene battery of quick charge |
| CN109135513A (en) * | 2018-09-13 | 2019-01-04 | 浙江加州国际纳米技术研究院台州分院 | Utilize aluminium triphosphate/nano silver composite conductive powder anti-static and anti-corrosive paint |
| CN109509879A (en) * | 2018-12-14 | 2019-03-22 | 桑顿新能源科技有限公司 | Clad anode material, preparation method and lithium ion battery altogether |
| CN112786859A (en) * | 2021-01-22 | 2021-05-11 | 合肥国轩高科动力能源有限公司 | Preparation method of tantalum-doped/porous metal nanoparticle-coated modified lithium iron phosphate material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101162776B (en) * | 2007-10-26 | 2010-06-02 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium iron phosphate suitable for high multiplying power electrokinetic cell and method for producing the same |
-
2009
- 2009-03-11 CN CN2009100378207A patent/CN101834287B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103337627A (en) * | 2013-06-14 | 2013-10-02 | 苏州诺信创新能源有限公司 | Lithium-ion battery and lithium iron phosphate positive electrode material for same |
| CN108258212A (en) * | 2018-01-03 | 2018-07-06 | 浙江衡远新能源科技有限公司 | A kind of lithium sulfur battery anode material preparation method |
| CN108550901A (en) * | 2018-05-11 | 2018-09-18 | 美澳视界（厦门）智能科技有限公司 | A kind of high-energy high density and the graphene battery of quick charge |
| CN109135513A (en) * | 2018-09-13 | 2019-01-04 | 浙江加州国际纳米技术研究院台州分院 | Utilize aluminium triphosphate/nano silver composite conductive powder anti-static and anti-corrosive paint |
| CN109135513B (en) * | 2018-09-13 | 2020-09-25 | 浙江加州国际纳米技术研究院台州分院 | Antistatic anticorrosive paint using aluminium triphosphate/nano silver composite conductive powder |
| CN109509879A (en) * | 2018-12-14 | 2019-03-22 | 桑顿新能源科技有限公司 | Clad anode material, preparation method and lithium ion battery altogether |
| CN112786859A (en) * | 2021-01-22 | 2021-05-11 | 合肥国轩高科动力能源有限公司 | Preparation method of tantalum-doped/porous metal nanoparticle-coated modified lithium iron phosphate material |
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| Publication number | Publication date |
|---|---|
| CN101834287B (en) | 2012-12-26 |
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Granted publication date: 20121226 Termination date: 20130311 |