CN107819120A - A kind of method that low cost prepares anode material for lithium-ion batteries - Google Patents
A kind of method that low cost prepares anode material for lithium-ion batteries Download PDFInfo
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- CN107819120A CN107819120A CN201711025538.8A CN201711025538A CN107819120A CN 107819120 A CN107819120 A CN 107819120A CN 201711025538 A CN201711025538 A CN 201711025538A CN 107819120 A CN107819120 A CN 107819120A
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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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- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a kind of method that low cost prepares lithium ion battery material, following steps are specifically included：Waste lithium iron phosphate positive electrode is used to prepare battery-level lithium carbonate and battery-grade iron phosphate for raw materials recovery first；Then LiFePO 4 material is prepared as raw material；Then silica is coated in LiFePO4 surface in situ using sol-gal process；Finally it is calcined with being placed in after glucose mixing and ball milling in atmosphere of inert gases, obtains the lithium iron phosphate battery positive material of nano silicon oxide/carbon coating.Positive electrode produced by the present invention has excellent high rate performance and cyclical stability.
Description
Technical field：
The present invention relates to lithium ion battery preparation field, is specifically related to a kind of low cost and prepares lithium ion cell positive material
The method of material.
Background technology：
With the rapid development of the national economy, the non-renewable energy resources using oil, coal, natural gas as representative gradually subtract
Few, atmosphere pollution, water pollution, noxious waste pollution constantly aggravate, and energy and environment problem is increasingly becoming sustainable development developable surface
The challenge faced.Based on this background, the exploitation of new energy deepens continuously, but the utilization of new energy be unable to do without accumulation power supply, so
The fast development of New Energy Industry provides unprecedented opportunities for application of the lithium ion battery in energy-storage battery field.Lithium from
Sub- battery because its have energy density is high, self discharge stream is small, it is safe, can high current charge-discharge, cycle-index be more, long lifespan
The advantages that, it is increasingly being applied to mobile phone, notebook computer, digital camera, electric automobile, Aero-Space, military equipment etc.
Multiple fields.But the life-span of lithium ion battery is generally 2-5, with the extensive use of lithium ion battery, can produce a large amount of
Waste and old lithium ion battery, not only result in resource serious waste, also there is certain pollution to environment and human body.
Patent 201610910138.4 discloses a kind of method that ferric phosphate and lithium carbonate are reclaimed in waste material from LiFePO4,
Precipitate to obtain lithium carbonate including oxidizing roasting, pole piece cleaning, the sour ball milling activation that phosphorates, pickling separation ferric phosphate, filtrate；Although should
Method can effectively reclaim ferric phosphate and lithium, but not only increase cost using substantial amounts of inorganic acid in this method, and right
Environment has certain harm.
The content of the invention：
It is an object of the invention to provide a kind of method that low cost prepares anode material for lithium-ion batteries, this method is with waste and old
Lithium iron phosphate positive material prepare anode material for lithium-ion batteries for raw materials recovery lithium and phosphoric acid iron reutilization, not only solve
The wasting of resources caused by battery is shelved, also a saving preparation cost, obtained electrode material good rate capability, charge-discharge performance
It is excellent.
To achieve the above object, the present invention uses following technical scheme：
A kind of method that low cost prepares anode material for lithium-ion batteries, comprises the following steps：
(1) waste lithium iron phosphate positive electrode is crushed, and carries out oxidizing roasting, processing is cooled to room temperature, mistake after terminating
Sieve, LiFePO4 raw material is made；
(2) concentrated sulfuric acid is added into LiFePO4 obtained above, adds decomposition accelerating agent, decomposition accelerating agent while stirring
After addition, continue to mix 1min, obtained mixture calcination processing, the solid that processing obtains after terminating adds deionization
Water, 30min is stirred by ultrasonic under conditions of 20-80 DEG C, 500W power, filter, into filtrate be added dropwise sodium hydroxide adjust pH to
1.5-2.5, filtering, raw phosphoric acid iron precipitation is obtained, and collect filtrate A, battery-grade iron phosphate is obtained after raw phosphoric acid ferrofining, it is standby
With；
(3) filtrate A to 90 DEG C made from heating stepses (2), and sodium carbonate is added, is filtered after precipitation, LITHIUM BATTERY carbon is made
Sour lithium is standby；
(4) battery-grade iron phosphate obtained above and battery-level lithium carbonate are mixed to add after deionized water stirs and turned
Milled processed in three-roll grinder is moved to, obtains mixed material, obtained mixed material is filtered through flame filter press, collects filter
Slag, dry, the solid reduction that is dried to obtain calcining, calcining is cooled to room temperature after terminating, the solid material after calcining using go from
Sub- water washing is dried to neutrality, obtains LiFePO 4 material；
(5) tetraethyl orthosilicate is added dropwise into absolute ethyl alcohol, then adds glacial acetic acid, triethylamine, is added after being well mixed
It is transferred to after stating obtained LiFePO 4 material in reactor, 10h is reacted at 150 DEG C, reaction is cooled to room temperature, mistake after terminating
Filter, after obtained solid is dried and it is placed in atmosphere of inert gases and calcines after glucose mixing and ball milling, obtain nano silicon oxide/carbon
The lithium iron phosphate cell material of cladding.
As the preferred of above-mentioned technical proposal, in step (1), the condition of the oxidizing roasting is：Calcining heat 600-700
DEG C, calcination time 0.5-2h.
As the preferred of above-mentioned technical proposal, in step (2), the decomposition accelerating agent is one in sodium sulphate, sodium chloride
Kind or two kinds of mixing.
As the preferred of above-mentioned technical proposal, in step (2), the LiFePO4, the concentrated sulfuric acid, the quality of decomposition accelerating agent
Than for 1：(0.6-1.2)：(0.01-0.2).
As the preferred of above-mentioned technical proposal, in step (2), the condition of the calcination processing is：Calcining heat 100-300
DEG C, calcination time 1-3h.
As the preferred of above-mentioned technical proposal, in step (3), the mol ratio of lithium is (1.1- in the sodium carbonate and filtrate
1.2)：1.
As the preferred of above-mentioned technical proposal, in step (4), the ferric phosphate, lithium carbonate, the mass ratio of deionized water are
1：0.15:0.5.
As the preferred of above-mentioned technical proposal, in step (4), the condition of the reduction calcining is：First with 10 DEG C/min
Heating rate be warming up to 500 DEG C, be incubated 2h, be then warming up to 750 DEG C with 6 DEG C/min heating rate, be incubated 6h.
As the preferred of above-mentioned technical proposal, in step (5), the absolute ethyl alcohol, tetraethyl orthosilicate, glacial acetic acid, three second
The volume ratio of amine is 30:0.5:5:1.
As the preferred of above-mentioned technical proposal, in step (5), the tetraethyl orthosilicate, LiFePO 4 material, glucose
Mass ratio is 0.01：1：(0.1-0.5).
Compared with prior art, the invention has the advantages that：
The present invention uses waste lithium iron phosphate positive electrode to prepare LiFePO 4 material for raw material to reclaim, in the mistake of recovery
Oxidizing roasting is carried out in journey first and effectively removes organic matter, is then added simultaneously necessarily during dense sulfuric acid treatment is added
Decomposition accelerating agent, water supersound process is directly added into after calcining, effectively reduces the usage amount of oxidant and acid in processing procedure, have
Effect has saved cost；
The present invention coats silica using sol-gal process in LiFePO 4 material surface in situ, is then mixed with glucose
Calcining, reasonable adjusting preparation condition, obtained anode material for lithium-ion batteries stability is good, and resistance to elevated temperatures is excellent, forthright again
Can be good, and there is good charge-discharge performance.
Embodiment：
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
The present invention is released, any restriction will not be formed to the present invention.
Embodiment 1
A kind of method that low cost prepares anode material for lithium-ion batteries, it is characterised in that comprise the following steps：
(1) waste lithium iron phosphate positive electrode is crushed, and carries out oxidizing roasting, processing is cooled to room temperature, mistake after terminating
Sieve, LiFePO4 raw material is made；Wherein, the condition of the oxidizing roasting is：600-700 DEG C of calcining heat, calcination time 0.5h；
(2) concentrated sulfuric acid is added into LiFePO4 obtained above, adds decomposition accelerating agent, decomposition accelerating agent while stirring
After addition, continue to mix 1min, obtained mixture calcination processing, the solid that processing obtains after terminating adds deionization
Water, 30min is stirred by ultrasonic under conditions of 20 DEG C, 500W power, filters, sodium hydroxide regulation pH to 1.5- is added dropwise into filtrate
2.5, filtering, raw phosphoric acid iron precipitation is obtained, and filtrate A is collected, and battery-grade iron phosphate is obtained after raw phosphoric acid ferrofining, it is standby；Its
In, the LiFePO4, the concentrated sulfuric acid, the mass ratio of decomposition accelerating agent are 1：0.6：0.01；The condition of the calcination processing is：Forge
Burn 100 DEG C of temperature, calcination time 3h；
(3) filtrate A to 90 DEG C made from heating stepses (2), and sodium carbonate is added, is filtered after precipitation, LITHIUM BATTERY carbon is made
Sour lithium is standby；
(4) battery-grade iron phosphate obtained above and battery-level lithium carbonate are mixed to add after deionized water stirs and turned
Milled processed in three-roll grinder is moved to, obtains mixed material, obtained mixed material is filtered through flame filter press, collects filter
Slag, dry, the solid reduction that is dried to obtain calcining, calcining is cooled to room temperature after terminating, the solid material after calcining using go from
Sub- water washing is dried to neutrality, obtains LiFePO 4 material；
(5) tetraethyl orthosilicate is added dropwise into absolute ethyl alcohol, then adds glacial acetic acid, triethylamine, is added after being well mixed
It is transferred to after stating obtained LiFePO 4 material in reactor, 10h is reacted at 150 DEG C, reaction is cooled to room temperature, mistake after terminating
Filter, after obtained solid is dried and it is placed in atmosphere of inert gases and calcines after glucose mixing and ball milling, obtain nano silicon oxide/carbon
The lithium iron phosphate cell material of cladding；Wherein, the tetraethyl orthosilicate, LiFePO 4 material, the mass ratio of glucose are 0.01：
1：0.1.
Embodiment 2
A kind of method that low cost prepares anode material for lithium-ion batteries, it is characterised in that comprise the following steps：
(1) waste lithium iron phosphate positive electrode is crushed, and carries out oxidizing roasting, processing is cooled to room temperature, mistake after terminating
Sieve, LiFePO4 raw material is made；Wherein, the condition of the oxidizing roasting is：600-700 DEG C of calcining heat, calcination time 2h；
(2) concentrated sulfuric acid is added into LiFePO4 obtained above, adds decomposition accelerating agent, decomposition accelerating agent while stirring
After addition, continue to mix 1min, obtained mixture calcination processing, the solid that processing obtains after terminating adds deionization
Water, 30min is stirred by ultrasonic under conditions of 80 DEG C, 500W power, filters, sodium hydroxide regulation pH to 1.5- is added dropwise into filtrate
2.5, filtering, raw phosphoric acid iron precipitation is obtained, and filtrate A is collected, and battery-grade iron phosphate is obtained after raw phosphoric acid ferrofining, it is standby；Its
In, the LiFePO4, the concentrated sulfuric acid, the mass ratio of decomposition accelerating agent are 1：1.2：0.2；The condition of the calcination processing is：Forge
Burn 300 DEG C of temperature, calcination time 3h；
(3) filtrate A to 90 DEG C made from heating stepses (2), and sodium carbonate is added, is filtered after precipitation, LITHIUM BATTERY carbon is made
Sour lithium is standby；
(4) battery-grade iron phosphate obtained above and battery-level lithium carbonate are mixed to add after deionized water stirs and turned
Milled processed in three-roll grinder is moved to, obtains mixed material, obtained mixed material is filtered through flame filter press, collects filter
Slag, dry, the solid reduction that is dried to obtain calcining, calcining is cooled to room temperature after terminating, the solid material after calcining using go from
Sub- water washing is dried to neutrality, obtains LiFePO 4 material；
(5) tetraethyl orthosilicate is added dropwise into absolute ethyl alcohol, then adds glacial acetic acid, triethylamine, is added after being well mixed
It is transferred to after stating obtained LiFePO 4 material in reactor, 10h is reacted at 150 DEG C, reaction is cooled to room temperature, mistake after terminating
Filter, after obtained solid is dried and it is placed in atmosphere of inert gases and calcines after glucose mixing and ball milling, obtain nano silicon oxide/carbon
The lithium iron phosphate cell material of cladding；Wherein, the tetraethyl orthosilicate, LiFePO 4 material, the mass ratio of glucose are 0.01：
1：0.5.
Embodiment 3
A kind of method that low cost prepares anode material for lithium-ion batteries, it is characterised in that comprise the following steps：
(1) waste lithium iron phosphate positive electrode is crushed, and carries out oxidizing roasting, processing is cooled to room temperature, mistake after terminating
Sieve, LiFePO4 raw material is made；Wherein, the condition of the oxidizing roasting is：600-700 DEG C of calcining heat, calcination time 1h；
(2) concentrated sulfuric acid is added into LiFePO4 obtained above, adds decomposition accelerating agent, decomposition accelerating agent while stirring
After addition, continue to mix 1min, obtained mixture calcination processing, the solid that processing obtains after terminating adds deionization
Water, 30min is stirred by ultrasonic under conditions of 30 DEG C, 500W power, filters, sodium hydroxide regulation pH to 1.5- is added dropwise into filtrate
2.5, filtering, raw phosphoric acid iron precipitation is obtained, and filtrate A is collected, and battery-grade iron phosphate is obtained after raw phosphoric acid ferrofining, it is standby；Its
In, the LiFePO4, the concentrated sulfuric acid, the mass ratio of decomposition accelerating agent are 1：0.7：0.05；The condition of the calcination processing is：Forge
Burn 200 DEG C of temperature, calcination time 1.5h；
(3) filtrate A to 90 DEG C made from heating stepses (2), and sodium carbonate is added, is filtered after precipitation, LITHIUM BATTERY carbon is made
Sour lithium is standby；
(4) battery-grade iron phosphate obtained above and battery-level lithium carbonate are mixed to add after deionized water stirs and turned
Milled processed in three-roll grinder is moved to, obtains mixed material, obtained mixed material is filtered through flame filter press, collects filter
Slag, dry, the solid reduction that is dried to obtain calcining, calcining is cooled to room temperature after terminating, the solid material after calcining using go from
Sub- water washing is dried to neutrality, obtains LiFePO 4 material；
(5) tetraethyl orthosilicate is added dropwise into absolute ethyl alcohol, then adds glacial acetic acid, triethylamine, is added after being well mixed
It is transferred to after stating obtained LiFePO 4 material in reactor, 10h is reacted at 150 DEG C, reaction is cooled to room temperature, mistake after terminating
Filter, after obtained solid is dried and it is placed in atmosphere of inert gases and calcines after glucose mixing and ball milling, obtain nano silicon oxide/carbon
The lithium iron phosphate cell material of cladding；Wherein, the tetraethyl orthosilicate, LiFePO 4 material, the mass ratio of glucose are 0.01：
1：0.2.
Embodiment 4
A kind of method that low cost prepares anode material for lithium-ion batteries, it is characterised in that comprise the following steps：
(1) waste lithium iron phosphate positive electrode is crushed, and carries out oxidizing roasting, processing is cooled to room temperature, mistake after terminating
Sieve, LiFePO4 raw material is made；Wherein, the condition of the oxidizing roasting is：600-700 DEG C of calcining heat, calcination time 1h；
(2) concentrated sulfuric acid is added into LiFePO4 obtained above, adds decomposition accelerating agent, decomposition accelerating agent while stirring
After addition, continue to mix 1min, obtained mixture calcination processing, the solid that processing obtains after terminating adds deionization
Water, 30min is stirred by ultrasonic under conditions of 40 DEG C, 500W power, filters, sodium hydroxide regulation pH to 1.5- is added dropwise into filtrate
2.5, filtering, raw phosphoric acid iron precipitation is obtained, and filtrate A is collected, and battery-grade iron phosphate is obtained after raw phosphoric acid ferrofining, it is standby；Its
In, the LiFePO4, the concentrated sulfuric acid, the mass ratio of decomposition accelerating agent are 1：0.8：0.15；The condition of the calcination processing is：Forge
Burn 200 DEG C of temperature, calcination time 2h；
(3) filtrate A to 90 DEG C made from heating stepses (2), and sodium carbonate is added, is filtered after precipitation, LITHIUM BATTERY carbon is made
Sour lithium is standby；
(4) battery-grade iron phosphate obtained above and battery-level lithium carbonate are mixed to add after deionized water stirs and turned
Milled processed in three-roll grinder is moved to, obtains mixed material, obtained mixed material is filtered through flame filter press, collects filter
Slag, dry, the solid reduction that is dried to obtain calcining, calcining is cooled to room temperature after terminating, the solid material after calcining using go from
Sub- water washing is dried to neutrality, obtains LiFePO 4 material；
(5) tetraethyl orthosilicate is added dropwise into absolute ethyl alcohol, then adds glacial acetic acid, triethylamine, is added after being well mixed
It is transferred to after stating obtained LiFePO 4 material in reactor, 10h is reacted at 150 DEG C, reaction is cooled to room temperature, mistake after terminating
Filter, after obtained solid is dried and it is placed in atmosphere of inert gases and calcines after glucose mixing and ball milling, obtain nano silicon oxide/carbon
The lithium iron phosphate cell material of cladding；Wherein, the tetraethyl orthosilicate, LiFePO 4 material, the mass ratio of glucose are 0.01：
1：0.3.
Embodiment 5
A kind of method that low cost prepares anode material for lithium-ion batteries, it is characterised in that comprise the following steps：
(1) waste lithium iron phosphate positive electrode is crushed, and carries out oxidizing roasting, processing is cooled to room temperature, mistake after terminating
Sieve, LiFePO4 raw material is made；Wherein, the condition of the oxidizing roasting is：600-700 DEG C of calcining heat, calcination time 1.5h；
(2) concentrated sulfuric acid is added into LiFePO4 obtained above, adds decomposition accelerating agent, decomposition accelerating agent while stirring
After addition, continue to mix 1min, obtained mixture calcination processing, the solid that processing obtains after terminating adds deionization
Water, 30min is stirred by ultrasonic under conditions of 60 DEG C, 500W power, filters, sodium hydroxide regulation pH to 1.5- is added dropwise into filtrate
2.5, filtering, raw phosphoric acid iron precipitation is obtained, and filtrate A is collected, and battery-grade iron phosphate is obtained after raw phosphoric acid ferrofining, it is standby；Its
In, the LiFePO4, the concentrated sulfuric acid, the mass ratio of decomposition accelerating agent are 1：1.0：0.2；The condition of the calcination processing is：Forge
Burn 300 DEG C of temperature, calcination time 2.5h；
(3) filtrate A to 90 DEG C made from heating stepses (2), and sodium carbonate is added, is filtered after precipitation, LITHIUM BATTERY carbon is made
Sour lithium is standby；
(4) battery-grade iron phosphate obtained above and battery-level lithium carbonate are mixed to add after deionized water stirs and turned
Milled processed in three-roll grinder is moved to, obtains mixed material, obtained mixed material is filtered through flame filter press, collects filter
Slag, dry, the solid reduction that is dried to obtain calcining, calcining is cooled to room temperature after terminating, the solid material after calcining using go from
Sub- water washing is dried to neutrality, obtains LiFePO 4 material；
(5) tetraethyl orthosilicate is added dropwise into absolute ethyl alcohol, then adds glacial acetic acid, triethylamine, is added after being well mixed
It is transferred to after stating obtained LiFePO 4 material in reactor, 10h is reacted at 150 DEG C, reaction is cooled to room temperature, mistake after terminating
Filter, after obtained solid is dried and it is placed in atmosphere of inert gases and calcines after glucose mixing and ball milling, obtain nano silicon oxide/carbon
The lithium iron phosphate cell material of cladding；Wherein, the tetraethyl orthosilicate, LiFePO 4 material, the mass ratio of glucose are 0.01：
1：0.4.
Anode material for lithium-ion batteries produced by the present invention is prepared into button cell, and carries out electrochemical property test, surveys
Test result shows that gram volume is 168mAh/g to positive electrode 0.1C of the invention first, and 1C electric discharge gram volumes are 152mAh/g；1C
2000 circulation residual capacities of discharge and recharge are more than 96%.
Claims (10)
1. a kind of method that low cost prepares anode material for lithium-ion batteries, it is characterised in that comprise the following steps：
(1) waste lithium iron phosphate positive electrode is crushed, and carries out oxidizing roasting, processing is cooled to room temperature after terminating, sieve, system
Obtain LiFePO4 raw material；
(2) concentrated sulfuric acid is added into LiFePO4 obtained above, adds decomposition accelerating agent while stirring, decomposition accelerating agent adds
After, continuing to mix 1min, obtained mixture calcination processing, the solid that processing obtains after terminating adds deionized water,
20-80 DEG C, 30min is stirred by ultrasonic under conditions of 500W power, filters, sodium hydroxide regulation pH to 1.5- is added dropwise into filtrate
2.5, filtering, raw phosphoric acid iron precipitation is obtained, and filtrate A is collected, and battery-grade iron phosphate is obtained after raw phosphoric acid ferrofining, it is standby；
(3) filtrate A to 90 DEG C made from heating stepses (2), and sodium carbonate is added, is filtered after precipitation, battery-level lithium carbonate is made
It is standby；
(4) battery-grade iron phosphate obtained above and battery-level lithium carbonate are mixed to add after deionized water stirs and are transferred to
Milled processed in three-roll grinder, obtains mixed material, and obtained mixed material is filtered through flame filter press, collects filter residue,
Dry, the solid reduction calcining being dried to obtain, calcining is cooled to room temperature after terminating, and the solid material after calcining uses deionized water
Washing is dried to neutrality, obtains LiFePO 4 material；
(5) tetraethyl orthosilicate is added dropwise into absolute ethyl alcohol, then adds glacial acetic acid, triethylamine, above-mentioned system is added after well mixed
It is transferred to after the LiFePO 4 material obtained in reactor, 10h is reacted at 150 DEG C, reaction is cooled to room temperature after terminating, and filters,
After obtained solid is dried and it is placed in atmosphere of inert gases and calcines after glucose mixing and ball milling, obtains nano silicon oxide/carbon bag
The lithium iron phosphate cell material covered.
2. the method that a kind of low cost as claimed in claim 1 prepares lithium ion battery material, it is characterised in that：Step (1)
In, the condition of the oxidizing roasting is：600-700 DEG C of calcining heat, calcination time 0.5-2h.
3. the method that a kind of low cost as claimed in claim 1 prepares lithium ion battery material, it is characterised in that：Step (2)
In, the decomposition accelerating agent is the mixing of one or both of sodium sulphate, sodium chloride.
4. the method that a kind of low cost as claimed in claim 1 prepares lithium ion battery material, it is characterised in that：Step (2)
In, the LiFePO4, the concentrated sulfuric acid, the mass ratio of decomposition accelerating agent are 1：(0.6-1.2)：(0.01-0.2).
5. the method that a kind of low cost as claimed in claim 1 prepares lithium ion battery material, it is characterised in that：Step (2)
In, the condition of the calcination processing is：100-300 DEG C of calcining heat, calcination time 1-3h.
6. the method that a kind of low cost as claimed in claim 1 prepares lithium ion battery material, it is characterised in that：Step (3)
In, the mol ratio of lithium is (1.1-1.2) in the sodium carbonate and filtrate：1.
7. the method that a kind of low cost as claimed in claim 1 prepares lithium ion battery material, it is characterised in that：Step (4)
In, the ferric phosphate, lithium carbonate, the mass ratio of deionized water are 1：0.15:0.5.
8. the method that a kind of low cost as claimed in claim 1 prepares lithium ion battery material, it is characterised in that：Step (4)
In, the condition of the reduction calcining is：Be warming up to 500 DEG C with 10 DEG C/min heating rate first, be incubated 2h, then with 6 DEG C/
Min heating rate is warming up to 750 DEG C, is incubated 6h.
9. the method that a kind of low cost as claimed in claim 1 prepares lithium ion battery material, it is characterised in that：Step (5)
In, the absolute ethyl alcohol, tetraethyl orthosilicate, glacial acetic acid, the volume ratio of triethylamine are 30:0.5:5:1.
10. the method that a kind of low cost as claimed in claim 1 prepares lithium ion battery material, it is characterised in that：Step (5)
In, the tetraethyl orthosilicate, LiFePO 4 material, the mass ratio of glucose are 0.01：1：(0.1-0.5).
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| CN201711025538.8A CN107819120A (en) | 2017-10-27 | 2017-10-27 | A kind of method that low cost prepares anode material for lithium-ion batteries |
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| CN201711025538.8A CN107819120A (en) | 2017-10-27 | 2017-10-27 | A kind of method that low cost prepares anode material for lithium-ion batteries |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109830772A (en) * | 2019-03-08 | 2019-05-31 | 胡茂宅 | A kind of regeneration method of LiFePO4 waste material |
| CN111285341A (en) * | 2020-02-21 | 2020-06-16 | 北京蒙京石墨新材料科技研究院有限公司 | Method for extracting battery-grade iron phosphate from waste lithium iron phosphate batteries |
| CN111326816A (en) * | 2018-12-14 | 2020-06-23 | 中国科学院深圳先进技术研究院 | Method for repairing lithium iron phosphate with assistance of oxidant |
| CN111653846A (en) * | 2020-07-27 | 2020-09-11 | 中南大学 | Treatment method of waste lithium iron phosphate battery |
| CN112047319A (en) * | 2020-09-11 | 2020-12-08 | 南昌航空大学 | Method for recovering battery-grade iron phosphate from waste iron phosphate slag |
| CN113193197A (en) * | 2021-04-26 | 2021-07-30 | 河北师范大学 | Preparation method of lithium iron phosphate additive for cathode material of commercial lithium battery |
| CN113571699A (en) * | 2021-09-26 | 2021-10-29 | 天津市职业大学 | Conductive phosphate anode material and preparation method thereof |
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- 2017-10-27 CN CN201711025538.8A patent/CN107819120A/en not_active Withdrawn
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| CN111326816A (en) * | 2018-12-14 | 2020-06-23 | 中国科学院深圳先进技术研究院 | Method for repairing lithium iron phosphate with assistance of oxidant |
| CN109830772A (en) * | 2019-03-08 | 2019-05-31 | 胡茂宅 | A kind of regeneration method of LiFePO4 waste material |
| CN109830772B (en) * | 2019-03-08 | 2020-10-30 | 湖南泰和美新能源科技有限公司 | Regeneration method of lithium iron phosphate waste |
| CN111285341A (en) * | 2020-02-21 | 2020-06-16 | 北京蒙京石墨新材料科技研究院有限公司 | Method for extracting battery-grade iron phosphate from waste lithium iron phosphate batteries |
| CN111653846A (en) * | 2020-07-27 | 2020-09-11 | 中南大学 | Treatment method of waste lithium iron phosphate battery |
| CN111653846B (en) * | 2020-07-27 | 2021-10-29 | 中南大学 | Treatment method of waste lithium iron phosphate battery |
| CN112047319A (en) * | 2020-09-11 | 2020-12-08 | 南昌航空大学 | Method for recovering battery-grade iron phosphate from waste iron phosphate slag |
| CN113193197A (en) * | 2021-04-26 | 2021-07-30 | 河北师范大学 | Preparation method of lithium iron phosphate additive for cathode material of commercial lithium battery |
| CN113193197B (en) * | 2021-04-26 | 2022-03-11 | 河北师范大学 | Preparation method of lithium iron phosphate additive for cathode material of commercial lithium battery |
| CN113571699A (en) * | 2021-09-26 | 2021-10-29 | 天津市职业大学 | Conductive phosphate anode material and preparation method thereof |
| CN114516628A (en) * | 2022-02-16 | 2022-05-20 | 松山湖材料实验室 | Modified lithium silicate and preparation method, application and product thereof |
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