CN109704300A - A kind of method of lithium iron phosphate battery positive material recycling and reusing - Google Patents
A kind of method of lithium iron phosphate battery positive material recycling and reusing Download PDFInfo
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Abstract
The present invention relates to field of lithium, disclose a kind of method of lithium iron phosphate battery positive material recycling and reusing.It comprises the following processes: (1) waste lithium iron phosphate battery being peelled off into shell after disassembling, be put into hydrogen peroxide and carry out sonic oscillation and mechanical stirring, take out aluminium foil and copper foil and diaphragm directly recycles, rest part is recovered liquid；(2) lithium source, source of iron and phosphorus source are added into recovered liquid, obtains mixed solution；(3) citric acid, ammonium hydroxide are added into mixed solution, forms colloidal sol；(4) powder for being spray-dried colloidal sol and carbon source mixing and ball milling, calcining are to get LiFePO 4 material.Method and process of the invention is simple, and product utilization rate is high, and cost recovery is low, gained LiFePO 4 material particle good sphericity, even particle size distribution, and tap density is high, stablizes under high magnification, and good conductivity, charge-discharge performance are excellent.
Description
Technical field
The present invention relates to field of lithium, disclose a kind of method of lithium iron phosphate battery positive material recycling and reusing.
Background technique
With the rapid development of the national economy, gradually subtracting using petroleum, coal, natural gas as the non-renewable energy resources of representative
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.Application of the fast development of New Energy Industry for lithium ion battery in energy-storage battery field provides unprecedented
Opportunity.
Lithium ion battery because it is high with energy density, self discharge stream is small, it is highly-safe, can high current charge-discharge, circulation
Often, the advantages that service life is long is increasingly being applied to mobile phone, laptop, digital camera, electric car, aviation boat
It, the multiple fields such as military equipment.But the service life of lithium ion battery is generally 2 ~ 5 years, with answering extensively for lithium ion battery
With can generate a large amount of waste and old lithium ion battery, not only result in resource serious waste, also have to environment and human body certain
Pollution.
LiFePO4 is the lithium-ion-power cell of positive electrode since its is at low cost, cycle performance is good, has a safety feature
The features such as, it has been widely applied to electric car industry.It is surprising that the consumption of huge lithium-ion-power cell brings number
Refuse battery, for these applying waste lithium ionic power batteries much directly as garbage disposal, this is not only a kind of waste of resource, and
And it pollutes the environment.Therefore, the recycling of lithium-ion-power cell has great importance.
Chinese invention patent application number 201510773893.8 discloses a kind of recycling of lithium iron phosphate dynamic battery
Method, step include: directly to recycle positive/negative plate, diaphragm and shell is isolated after lithium iron phosphate dynamic battery electric discharge, dismantling
Diaphragm and shell；Through ultrasound, stir process after negative electrode tab crushing, copper sheet is recycled after filtering.Positive plate pulverize and sieve after using having
Machine acid solution carries out Leach reaction, realizes after filtering and separates containing lithium, aluminum solutions with filter residues such as organic acid molysite, carbon black, binders；To
Lye is added in filtrate, obtain aluminum hydroxide precipitation and is separated with lithium-containing solution；Lithium will can be recycled after the processing of gained lithium-containing solution；It is heavy
Solution after lithium obtains organic acid sodium salt product by crystallisation step.Method described in the invention is directly soaked using organic acid solution
The iron etc. in LiFePO4 positive plate is separated out, simplifies recovery process, and using conventional equipment and raw material, economy is easily returned
Lithium, aluminium and the copper in lithium iron phosphate battery positive material are received, and has obtained the organic acid sodium salt product with high added value.
Chinese invention patent application number 201810037663.9 discloses a kind of dynamic suitable for LiFePO4/nickle cobalt lithium manganate
The method of power recycling and reusing of batteries, in this method, LiFePO4/nickle cobalt lithium manganate reparation recovery method includes the following steps:
Forced electric discharge, forces extruding, separating twice, forced air drying, vibrosieve, high-temperature calcination, pickling, alkali soak, is secondary at first crushing
Forced air drying, measurement constituent content, secondary high-temperature calcining；The regeneration recovery method of LiFePO4 includes the following steps: to force to put
Electricity, forces extruding, separating twice, forced air drying, vibrosieve, high-temperature calcination, pickling, alkali to soak two, post-blast at first crushing
It is dry；The regeneration recovery method of nickle cobalt lithium manganate includes the following steps: forced electric discharge, first crushing, forces extruding, two wheat-middlings
Vibrosieve, high-temperature calcination, pickling, plating, carbanion is added in broken, forced air drying；The present invention it is simple and practical, recycling at
This is low, and non-contaminating pressure, applicability and strong operability, can be used for industrialized production.
According to above-mentioned, in existing scheme for recycling lithium iron phosphate battery positive material method, technique is cumbersome, produces
Product utilization rate is low, and salvage material poorly conductive, and high magnification stability is poor, and charge-discharge performance is undesirable.
Summary of the invention
The technical method of the wider recycling lithium iron phosphate battery positive material of application at present, cumbersome, production that there are techniques
The low defect of product utilization rate, and the poorly conductive of product is recycled, high magnification stability is poor, and charge-discharge performance is undesirable, this hair
It is bright to propose a kind of method of lithium iron phosphate battery positive material recycling and reusing, it can effectively solve above-mentioned technical problem.
To solve the above problems, the invention adopts the following technical scheme:
A kind of method of lithium iron phosphate battery positive material recycling and reusing, the detailed process of preparation are as follows:
(1) waste lithium iron phosphate battery is first peelled off into battery case after disassembling, then by the part one other than shell in addition to the battery
It rises and is put into hydrogen peroxide, including positive plate, negative electrode tab, diaphragm, electrolyte and the conductive agent separated, hydrogen peroxide usage amount makes just
Subject to submergence, sonic oscillation and mechanical stirring are then used, until positive and negative anodes powder is kept completely separate with pole piece, takes out aluminium foil and copper
Foil and diaphragm directly recycle, and rest part is recovered liquid；
(2) lithium source, source of iron and phosphorus source are added in the recovered liquid obtained to step (1), obtains mixed solution；
(3) under conditions of heating water bath stirs, citric acid is added in the mixed solution that obtains to step (2), while matter is added
Measuring the ammonium hydroxide that concentration is 20% ~ 30% and adjusting pH value is 7 ~ 8, is stirred continuously, until forming colloidal sol；
(4) under stirring, first the colloidal sol that step (3) obtains is spray-dried, powder is collected, is then mixed with carbon source
Carry out high-energy ball milling, then ball milling product be placed in tube furnace and is calcined, it is cooling, discharging to get LiFePO 4 material, complete for
The recycling and reusing of lithium iron phosphate battery positive material.
Preferably, the power of sonic oscillation described in step (1) is 30 ~ 40kHz.In order to solve cost, hydrogen peroxide is used
Amount makes just to submerge subject to yield.
Preferably, churned mechanically stirring rate described in step (1) is 200 ~ 300r/min.
Preferably, step (2) lithium source is at least one of lithium carbonate, lithium hydroxide, lithium acetate.
Preferably, step (2) source of iron is ferrous sulfate.
Preferably, step (2) phosphorus source is phosphoric acid, in ammonium dihydrogen phosphate, disodium-hydrogen, sodium phosphate, potassium phosphate
It is at least one.
Preferably, in step (2) described mixed solution, Li+、Fe2+、PO4 3-Molar ratio be 1:1:1.
Preferably, in step (3) the heating water bath stirring, temperature is 50 ~ 70 DEG C, and revolving speed is 200 ~ 300r/min, when
Between be 6 ~ 8h.
Sol method is a kind of method for preparing colloid, and sol method, which prepares ferric lithium phosphate precursor, so that raw material is reached molecule
Horizontal mixing, preparation temperature is low, and obtained positive electrode conducts electricity very well, and dynamics is small and is evenly distributed.
Preferably, in step (3), the additional amount of citric acid is the 3 ~ 6% of mixed solution weight.
Preferably, step (4) carbon source is acetylene carbon black, graphitic carbon black, superconduction carbon black, at least one in graphene
Kind, the additional amount of carbon source is 5 ~ 15% of powder weight after being spray-dried.
Spray drying is a kind of method that systematization technique is applied to dry materials, by solvent or diluent through being atomized in hothouse
Afterwards, in the contact with hot-air, moisture rapid vaporization to get arrive dry products；The method can directly make solution, emulsion, coagulate
The dry powdering of glue or particulate preparation, can save the processes such as devaporation, crushing.The present invention use spray drying technology, pass through by
Ferric lithium phosphate precursor is prepared into spheric granules, can guarantee the continuity of technique and the uniformity of material, reduces production cost, mentions
The electric conductivity of high material tap density and LiFePO 4 material.Preferably, the pressure of step (4) described spray drying be 20 ~
40MPa, time are 3 ~ 5h.
Preferably, the revolving speed of step (4) described high-energy ball milling is 2000 ~ 2100r/min, and the time is 2 ~ 3h.
Preferably, step (4) calcining carries out in nitrogen atmosphere, and temperature is 400 ~ 600 DEG C, and the time is 2 ~ 6h.
By a kind of method for lithium iron phosphate battery positive material recycling and reusing that above content provides, by waste and old ferric phosphate
Lithium battery peels off battery case after disassembling, and is then soaked into hydrogen peroxide, i.e., by the part other than shell in addition to the battery, separates
Positive plate, negative electrode tab, diaphragm, electrolyte and conductive agent be put into togerther in hydrogen peroxide, using sonic oscillation and mechanical stirring, make
It obtains positive and negative anodes powder to efficiently separate with pole piece, takes out aluminium foil and copper foil and diaphragm directly recycles, rest part is mixed solution；
Into mixed liquor, supplement adds lithium source, source of iron and phosphorus source, is stirred continuously under water bath condition, and citric acid is added, and adjusts in ammonium hydroxide
Under pH, stirring forms colloidal sol；Under stirring, colloidal sol is spray-dried, collects powder, and carbon source high-energy ball milling, most
It is placed in tube furnace, is calcined under nitrogen atmosphere, collect product.
The present invention provides a kind of methods of lithium iron phosphate battery positive material recycling and reusing, compared with prior art,
Its feature protruded and excellent effect are:
1, it proposes to combine using sol method, spray drying and calcining and carries out lithium iron phosphate battery positive material recycling and reusing
Method.
2, after by directly being separated the ingredient in LiFePO4 refuse battery, ferric phosphate is prepared using sol method recycling
Lithium material, product utilization rate is high, does not need the cumbersome processes such as pickling separation, filtrate precipitating, reduces the use of a large amount of inorganic acids,
Cost recovery is saved, the cleaning for realizing LiFePO4 recycles.
3, by using the technology of spray drying, so that the LiFePO 4 material particle good sphericity of preparation, size distribution
Uniformly, more stable under high magnification to promote the tap density of material.
4, by carrying out carbon coating in LiFePO 4 material appearance, resulting materials good conductivity, charge-discharge performance is excellent.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
(1) waste lithium iron phosphate battery is first peelled off into battery case after disassembling, then by the part one other than shell in addition to the battery
It rises and is put into hydrogen peroxide, including positive plate, negative electrode tab, diaphragm, electrolyte and the conductive agent separated, hydrogen peroxide usage amount makes back
Material is just subject to submergence；Then sonic oscillation and mechanical stirring are used, the power of sonic oscillation is 35kHz, churned mechanically stirring
Rate is 250r/min, so that positive and negative anodes powder is kept completely separate with pole piece, takes out aluminium foil and copper foil and diaphragm directly recycles,
Remaining part is divided into recovered liquid；
(2) lithium source, source of iron and phosphorus source are added in the recovered liquid obtained to step (1), obtains mixed solution；Lithium source is hydroxide
Lithium；Source of iron is ferrous sulfate；Phosphorus source is ammonium dihydrogen phosphate；In mixed solution, Li+、Fe2+、PO4 3-Molar ratio be 1:1:1；
(3) under conditions of heating water bath stirs, citric acid is added in the mixed solution that obtains to step (2), while matter is added
Measuring the ammonium hydroxide that concentration is 25% and adjusting pH value is 8, is stirred continuously, until forming colloidal sol；In heating water bath stirring, temperature is 65 DEG C,
Revolving speed is 280r/min, time 6.5h；In colloidal sol, the additional amount of citric acid is the 5% of mixed solution weight；
(4) under stirring, first the colloidal sol that step (3) obtains is spray-dried, the pressure of spray drying is 30MPa,
Time is 4h, collects powder, then mixes with carbon source and carries out high-energy ball milling, then ball milling product is placed in tube furnace and is calcined, cold
But, it discharges to get LiFePO 4 material, completes the recycling and reusing for lithium iron phosphate battery positive material；Carbon source is graphite
Carbon black, the additional amount of carbon source are 12% of powder weight after being spray-dried；The revolving speed of high-energy ball milling is 2080r/min, and the time is
2h；Calcining carries out in nitrogen atmosphere, and temperature is 550 DEG C, time 3h.
Embodiment 2
(1) waste lithium iron phosphate battery is first peelled off into battery case after disassembling, then by the part one other than shell in addition to the battery
It rises and is put into hydrogen peroxide, including positive plate, negative electrode tab, diaphragm, electrolyte and the conductive agent separated, hydrogen peroxide usage amount makes back
Material is just subject to submergence；Then sonic oscillation and mechanical stirring are used, the power of sonic oscillation is 30kHz, churned mechanically stirring
Rate is 300r/min, so that positive and negative anodes powder is kept completely separate with pole piece, takes out aluminium foil and copper foil and diaphragm directly recycles,
Remaining part is divided into recovered liquid；
(2) lithium source, source of iron and phosphorus source are added in the recovered liquid obtained to step (1), obtains mixed solution；Lithium source is lithium carbonate；
Source of iron is ferrous sulfate；Phosphorus source is phosphoric acid；In mixed solution, Li+、Fe2+、PO4 3-Molar ratio be 1:1:1；
(3) under conditions of heating water bath stirs, citric acid is added in the mixed solution that obtains to step (2), while matter is added
Measuring the ammonium hydroxide that concentration is 24% and adjusting pH value is 7, is stirred continuously, until forming colloidal sol；In heating water bath stirring, temperature is 55 DEG C,
Revolving speed is 220r/min, time 7.5h；In colloidal sol, the additional amount of citric acid is the 4% of mixed solution weight；
(4) under stirring, first the colloidal sol that step (3) obtains is spray-dried, the pressure of spray drying is 27MPa,
Time is 3h, collects powder, then mixes with carbon source and carries out high-energy ball milling, then ball milling product is placed in tube furnace and is calcined, cold
But, it discharges to get LiFePO 4 material, completes the recycling and reusing for lithium iron phosphate battery positive material；Carbon source is acetylene
Carbon black, the additional amount of carbon source are 7% of powder weight after being spray-dried；The revolving speed of high-energy ball milling is 2020r/min, time 3h；
Calcining carries out in nitrogen atmosphere, and temperature is 450 DEG C, time 5h.
Embodiment 3
(1) waste lithium iron phosphate battery is first peelled off into battery case after disassembling, then by the part one other than shell in addition to the battery
It rises and is put into hydrogen peroxide, including positive plate, negative electrode tab, diaphragm, electrolyte and the conductive agent separated, hydrogen peroxide usage amount makes back
Material is just subject to submergence；Then sonic oscillation and mechanical stirring are used, the power of sonic oscillation is 40kHz, churned mechanically stirring
Rate is 200r/min, so that positive and negative anodes powder is kept completely separate with pole piece, takes out aluminium foil and copper foil and diaphragm directly recycles,
Remaining part is divided into recovered liquid；
(2) lithium source, source of iron and phosphorus source are added in the recovered liquid obtained to step (1), obtains mixed solution；Lithium source is lithium acetate；
Source of iron is ferrous sulfate；Phosphorus source is disodium-hydrogen；In mixed solution, Li+、Fe2+、PO4 3-Molar ratio be 1:1:1；
(3) under conditions of heating water bath stirs, citric acid is added in the mixed solution that obtains to step (2), while matter is added
Measuring the ammonium hydroxide that concentration is 28% and adjusting pH value is 8, is stirred continuously, until forming colloidal sol；In heating water bath stirring, temperature is 70 DEG C,
Revolving speed is 300r/min, time 6h；In colloidal sol, the additional amount of citric acid is the 6% of mixed solution weight；
(4) under stirring, first the colloidal sol that step (3) obtains is spray-dried, the pressure of spray drying is 35MPa,
Time is 5h, collects powder, then mixes with carbon source and carries out high-energy ball milling, then ball milling product is placed in tube furnace and is calcined, cold
But, it discharges to get LiFePO 4 material, completes the recycling and reusing for lithium iron phosphate battery positive material；Carbon source is superconduction
Carbon black, the additional amount of carbon source are 15% of powder weight after being spray-dried；The revolving speed of high-energy ball milling is 2100r/min, and the time is
2h；Calcining carries out in nitrogen atmosphere, and temperature is 600 DEG C, time 2h.
Embodiment 4
(1) waste lithium iron phosphate battery is first peelled off into battery case after disassembling, then by the part one other than shell in addition to the battery
It rises and is put into hydrogen peroxide, including positive plate, negative electrode tab, diaphragm, electrolyte and the conductive agent separated, hydrogen peroxide usage amount makes back
Material is just subject to submergence；Then sonic oscillation and mechanical stirring are used, the power of sonic oscillation is 32kHz, churned mechanically stirring
Rate is 260r/min, so that positive and negative anodes powder is kept completely separate with pole piece, takes out aluminium foil and copper foil and diaphragm directly recycles,
Remaining part is divided into recovered liquid；
(2) lithium source, source of iron and phosphorus source are added in the recovered liquid obtained to step (1), obtains mixed solution；Lithium source is lithium carbonate；
Source of iron is ferrous sulfate；Phosphorus source is sodium phosphate；In mixed solution, Li+、Fe2+、PO4 3-Molar ratio be 1:1:1；
(3) under conditions of heating water bath stirs, citric acid is added in the mixed solution that obtains to step (2), while matter is added
Measuring the ammonium hydroxide that concentration is 22% and adjusting pH value is 7, is stirred continuously, until forming colloidal sol；In heating water bath stirring, temperature is 50 DEG C,
Revolving speed is 200r/min, time 8h；In colloidal sol, the additional amount of citric acid is the 3% of mixed solution weight；
(4) under stirring, first the colloidal sol that step (3) obtains is spray-dried, the pressure of spray drying is 20MPa,
Time is 5h, collects powder, then mixes with carbon source and carries out high-energy ball milling, then ball milling product is placed in tube furnace and is calcined, cold
But, it discharges to get LiFePO 4 material, completes the recycling and reusing for lithium iron phosphate battery positive material；Carbon source is graphite
Alkene, the additional amount of carbon source are 5% of powder weight after being spray-dried；The revolving speed of high-energy ball milling is 2000r/min, time 3h；It forges
Burning carries out in nitrogen atmosphere, and temperature is 400 DEG C, time 6h.
Embodiment 5
(1) waste lithium iron phosphate battery is first peelled off into battery case after disassembling, then by the part one other than shell in addition to the battery
It rises and is put into hydrogen peroxide, including positive plate, negative electrode tab, diaphragm, electrolyte and the conductive agent separated, hydrogen peroxide usage amount makes back
Material is just subject to submergence；Then sonic oscillation and mechanical stirring are used, the power of sonic oscillation is 38kHz, churned mechanically stirring
Rate is 210r/min, so that positive and negative anodes powder is kept completely separate with pole piece, takes out aluminium foil and copper foil and diaphragm directly recycles,
Remaining part is divided into recovered liquid；
(2) lithium source, source of iron and phosphorus source are added in the recovered liquid obtained to step (1), obtains mixed solution；Lithium source is hydroxide
Lithium；Source of iron is ferrous sulfate；Phosphorus source is potassium phosphate；In mixed solution, Li+、Fe2+、PO4 3-Molar ratio be 1:1:1；
(3) under conditions of heating water bath stirs, citric acid is added in the mixed solution that obtains to step (2), while matter is added
Measuring the ammonium hydroxide that concentration is 24% and adjusting pH value is 7.5, is stirred continuously, until forming colloidal sol；In heating water bath stirring, temperature 508
DEG C, revolving speed 260r/min, time 7h；In colloidal sol, the additional amount of citric acid is the 5% of mixed solution weight；
(4) under stirring, first the colloidal sol that step (3) obtains is spray-dried, the pressure of spray drying is 25MPa,
Time is 4h, collects powder, then mixes with carbon source and carries out high-energy ball milling, then ball milling product is placed in tube furnace and is calcined, cold
But, it discharges to get LiFePO 4 material, completes the recycling and reusing for lithium iron phosphate battery positive material；Carbon source is acetylene
Carbon black, the additional amount of carbon source are 11% of powder weight after being spray-dried；The revolving speed of high-energy ball milling is 2060r/min, and the time is
2.5h；Calcining carries out in nitrogen atmosphere, and temperature is 480 DEG C, time 3h.
Embodiment 6
(1) waste lithium iron phosphate battery is first peelled off into battery case after disassembling, then by the part one other than shell in addition to the battery
It rises and is put into hydrogen peroxide, including positive plate, negative electrode tab, diaphragm, electrolyte and the conductive agent separated, hydrogen peroxide usage amount makes back
Material is just subject to submergence；Then sonic oscillation and mechanical stirring are used, the power of sonic oscillation is 33kHz, churned mechanically stirring
Rate is 290r/min, so that positive and negative anodes powder is kept completely separate with pole piece, takes out aluminium foil and copper foil and diaphragm directly recycles,
Remaining part is divided into recovered liquid；
(2) lithium source, source of iron and phosphorus source are added in the recovered liquid obtained to step (1), obtains mixed solution；Lithium source is lithium acetate；
Source of iron is ferrous sulfate；Phosphorus source is phosphoric acid；In mixed solution, Li+、Fe2+、PO4 3-Molar ratio be 1:1:1；
(3) under conditions of heating water bath stirs, citric acid is added in the mixed solution that obtains to step (2), while matter is added
Measuring the ammonium hydroxide that concentration is 27% and adjusting pH value is 7 ~ 8, is stirred continuously, until forming colloidal sol；In heating water bath stirring, temperature 60
DEG C, revolving speed 250r/min, time 7h；In colloidal sol, the additional amount of citric acid is the 4% of mixed solution weight；
(4) under stirring, first the colloidal sol that step (3) obtains is spray-dried, the pressure of spray drying is 28MPa,
Time is 5h, collects powder, then mixes with carbon source and carries out high-energy ball milling, then ball milling product is placed in tube furnace and is calcined, cold
But, it discharges to get LiFePO 4 material, completes the recycling and reusing for lithium iron phosphate battery positive material；Carbon source is graphite
Carbon black, the additional amount of carbon source are 10% of powder weight after being spray-dried；The revolving speed of high-energy ball milling is 2050r/min, and the time is
2.5h；Calcining carries out in nitrogen atmosphere, and temperature is 500 DEG C, time 4h.
Comparative example 1
Comparative example 1 is directly to fire the commercially available carbon dope LiFePO 4 material of synthesis.
The LiFePO4 of embodiment recycling and commercially available LiFePO4 are under equal conditions prepared into test battery, carried out pair
Than analysis, test method are as follows:
By LiFePO4, conductive agent, slurry is carried out according to mass ratio 93: 2: 5, then by slurry coating on aluminium foil, drying is obtained
To positive plate；Using hard carbon as cathode；2400 microporous polypropylene membrane of Celgard is diaphragm；1mol/L LiPF6- EC/DMC electrolysis
Liquid is assembled into test battery；In 1C multiplying power electric discharge specific capacity.By test analysis, the LiFePO4 of recycling is recycled, property
It can be substantially close to the LiFePO4 newly fired.Such as table 1:
Table 1:
Claims (10)
1. a kind of method of lithium iron phosphate battery positive material recycling and reusing, which is characterized in that the detailed process of preparation are as follows:
(1) waste lithium iron phosphate battery is first peelled off into battery case after disassembling, then by the part one other than shell in addition to the battery
It rises and is put into hydrogen peroxide, hydrogen peroxide usage amount makes subject to just submergence;Then sonic oscillation and mechanical stirring are used, until positive and negative anodes
Powder is kept completely separate with pole piece, takes out aluminium foil and copper foil and diaphragm directly recycles, rest part is recovered liquid；
(2) lithium source, source of iron and phosphorus source are added in the recovered liquid obtained to step (1), obtains mixed solution；
(3) under conditions of heating water bath stirs, citric acid is added in the mixed solution that obtains to step (2), while matter is added
Measuring the ammonium hydroxide that concentration is 20% ~ 30% and adjusting pH value is 7 ~ 8, is stirred continuously, until forming colloidal sol；
(4) under stirring, first the colloidal sol that step (3) obtains is spray-dried, powder is collected, is then mixed with carbon source
Carry out high-energy ball milling, then ball milling product be placed in tube furnace and is calcined, it is cooling, discharging to get LiFePO 4 material, complete for
The recycling and reusing of lithium iron phosphate battery positive material.
2. a kind of method of lithium iron phosphate battery positive material recycling and reusing according to claim 1, it is characterised in that: step
Suddenly the power of sonic oscillation described in (1) is 30 ~ 40kHz.
3. a kind of method of lithium iron phosphate battery positive material recycling and reusing according to claim 1, it is characterised in that: step
Suddenly churned mechanically stirring rate described in (1) is 200 ~ 300r/min.
4. a kind of method of lithium iron phosphate battery positive material recycling and reusing according to claim 1, it is characterised in that: step
Suddenly (2) described lithium source is at least one of lithium carbonate, lithium hydroxide, lithium acetate；Source of iron is ferrous sulfate；Phosphorus source be phosphoric acid,
At least one of ammonium dihydrogen phosphate, disodium-hydrogen, sodium phosphate, potassium phosphate.
5. according to claim 1 or a kind of 4 methods of lithium iron phosphate battery positive material recycling and reusing, feature exist
In: in step (2) described mixed solution, Li+、Fe2+、PO4 3-Molar ratio be 1:1:1.
6. a kind of method of lithium iron phosphate battery positive material recycling and reusing according to claim 1, it is characterised in that: step
Suddenly in (3) described heating water bath stirring, temperature is 50 ~ 70 DEG C, and revolving speed is 200 ~ 300r/min, and the time is 6 ~ 8h.
7. a kind of method of lithium iron phosphate battery positive material recycling and reusing according to claim 1, it is characterised in that: step
Suddenly in (3), the additional amount of citric acid is the 3 ~ 6% of mixed solution weight.
8. a kind of method of lithium iron phosphate battery positive material recycling and reusing according to claim 1, it is characterised in that: step
Suddenly (4) described carbon source is at least one of acetylene carbon black, graphitic carbon black, superconduction carbon black, graphene, and the additional amount of carbon source is spray
The 5 ~ 15% of powder weight after mist is dry.
9. a kind of method of lithium iron phosphate battery positive material recycling and reusing according to claim 1, it is characterised in that: step
Suddenly the pressure of (4) described spray drying is 20 ~ 40MPa, and the time is 3 ~ 5h；The revolving speed of the high-energy ball milling is 2000 ~ 2100r/
Min, time are 2 ~ 3h.
10. a kind of method of lithium iron phosphate battery positive material recycling and reusing according to claim 1, it is characterised in that:
Step (4) calcining carries out in nitrogen atmosphere, and temperature is 400 ~ 600 DEG C, and the time is 2 ~ 6h.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111187913A (en) * | 2020-02-20 | 2020-05-22 | 广东省稀有金属研究所 | Method for selectively recovering lithium and copper in waste lithium iron phosphate batteries |
| CN112599766A (en) * | 2020-12-14 | 2021-04-02 | 台州市宸明新能源科技有限公司 | Regeneration process of waste lithium iron phosphate battery positive electrode material |
| CN112707378A (en) * | 2020-12-25 | 2021-04-27 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Recovery method and application of lithium iron phosphate positive plate |
| CN113161524A (en) * | 2021-04-19 | 2021-07-23 | 东北师范大学 | Composite positive electrode material obtained by utilizing waste lithium iron phosphate batteries and method and application thereof |
| CN113381089A (en) * | 2021-06-30 | 2021-09-10 | 湖北融通高科先进材料有限公司 | Method for preparing nano lithium iron phosphate material by recycling ferrous phosphate |
| CN115148483A (en) * | 2022-07-28 | 2022-10-04 | 中国科学院生态环境研究中心 | Preparation of LiFe by using waste lithium iron phosphate battery 5 O 8 Method for producing magnetic material |
| CN115259125A (en) * | 2022-01-25 | 2022-11-01 | 中国科学院过程工程研究所 | Recovery and regeneration method of lithium iron phosphate reclaimed material and lithium iron phosphate material |
| CN115385322A (en) * | 2022-10-31 | 2022-11-25 | 沧州彩客新能源有限公司 | Preparation method and system of lithium iron phosphate anode material |
| CN115818607A (en) * | 2021-10-11 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Method for recycling lithium iron phosphate material |
-
2018
- 2018-12-20 CN CN201811562057.5A patent/CN109704300A/en not_active Withdrawn
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111187913B (en) * | 2020-02-20 | 2021-07-02 | 广东省稀有金属研究所 | Method for selectively recovering lithium and copper in waste lithium iron phosphate batteries |
| CN111187913A (en) * | 2020-02-20 | 2020-05-22 | 广东省稀有金属研究所 | Method for selectively recovering lithium and copper in waste lithium iron phosphate batteries |
| CN112599766B (en) * | 2020-12-14 | 2023-04-25 | 台州市宸明新能源科技有限公司 | Regeneration process of waste lithium iron phosphate battery anode material |
| CN112599766A (en) * | 2020-12-14 | 2021-04-02 | 台州市宸明新能源科技有限公司 | Regeneration process of waste lithium iron phosphate battery positive electrode material |
| CN112707378A (en) * | 2020-12-25 | 2021-04-27 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Recovery method and application of lithium iron phosphate positive plate |
| CN113161524A (en) * | 2021-04-19 | 2021-07-23 | 东北师范大学 | Composite positive electrode material obtained by utilizing waste lithium iron phosphate batteries and method and application thereof |
| CN113161524B (en) * | 2021-04-19 | 2024-04-26 | 东北师范大学 | Composite positive electrode material obtained by utilizing waste lithium iron phosphate battery, and method and application thereof |
| CN113381089B (en) * | 2021-06-30 | 2022-08-30 | 湖北融通高科先进材料有限公司 | Method for preparing nano lithium iron phosphate material by recycling ferrous phosphate |
| CN113381089A (en) * | 2021-06-30 | 2021-09-10 | 湖北融通高科先进材料有限公司 | Method for preparing nano lithium iron phosphate material by recycling ferrous phosphate |
| CN115818607A (en) * | 2021-10-11 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Method for recycling lithium iron phosphate material |
| CN115818607B (en) * | 2021-10-11 | 2023-10-31 | 宁德时代新能源科技股份有限公司 | Method for recycling lithium iron phosphate material |
| CN115259125A (en) * | 2022-01-25 | 2022-11-01 | 中国科学院过程工程研究所 | Recovery and regeneration method of lithium iron phosphate reclaimed material and lithium iron phosphate material |
| CN115148483A (en) * | 2022-07-28 | 2022-10-04 | 中国科学院生态环境研究中心 | Preparation of LiFe by using waste lithium iron phosphate battery 5 O 8 Method for producing magnetic material |
| CN115385322A (en) * | 2022-10-31 | 2022-11-25 | 沧州彩客新能源有限公司 | Preparation method and system of lithium iron phosphate anode material |
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Application publication date: 20190503 |