CN109167119A - Titanium doped regeneration lithium iron phosphate positive material of one kind and preparation method thereof, application - Google Patents
Titanium doped regeneration lithium iron phosphate positive material of one kind and preparation method thereof, application Download PDFInfo
- Publication number
- CN109167119A CN109167119A CN201810952828.5A CN201810952828A CN109167119A CN 109167119 A CN109167119 A CN 109167119A CN 201810952828 A CN201810952828 A CN 201810952828A CN 109167119 A CN109167119 A CN 109167119A
- Authority
- CN
- China
- Prior art keywords
- lithium
- source
- titanium
- positive material
- iron phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of preparation methods of titanium doped regeneration lithium iron phosphate positive material, steps are as follows: after lithium source, source of iron, titanium source, phosphorus source, carbon source is added in recycling lithium iron phosphate battery positive material, obtain doped products, lithium source, source of iron, titanium source, the lithium in phosphorus source, iron, titanium, P elements molar ratio be 1:0.9-0.99:0.1-0.01:1；Solvent medium is added in precursor, obtains intermediary after mixing；Under an inert atmosphere, regeneration positive electrode is made by being calcined in intermediary.Titanium doped regeneration lithium iron phosphate positive material of the invention is applied in lithium ion battery as positive electrode active materials, has excellent electro-chemical activity and cyclical stability.
Description
Technical field
The present invention relates to a kind of titanium doped regeneration lithium iron phosphate positive materials and preparation method thereof, application, belong to discarded electricity
The reclaiming technical field of pond material.
Background technique
With investment and promotion that country develops new-energy automobile, the yield of electric automobile power battery is greatly improved,
Accompanying problem is that the taking back and process of discarded power battery, the solution of the problem not only contribute to the protection of environment, more
Be conducive to recycling for resource, be of great immediate significance.
Due to LiFePO4 (LiFePO4) power battery performance stabilization, it is widely used in recent years, but due to waste and old phosphoric acid
For iron lithium material without containing precious metals such as cobalt, nickel, recycling value is relatively low, is returned using existing recovery process
It receives without economic benefit, so the main stream approach that reparative regeneration method is handled at current waste lithium iron phosphate battery, has very high
Recycle benefit, comprehensive resource utilization rate highest.
Existing document report can repair positive electrode by simply supplementing lithium and ferro element at present, still, pass through
The discharge capacity of the regenerated lithium iron phosphate positive material of method is smaller at present, and cycle-index is shorter when test, capacity attenuation rate compared with
Greatly.
It is well known that lithium iron phosphate dynamic battery required generally for the various aspects technical indicator of positive electrode it is higher,
It is particularly important to develop new waste and old lithium ion battery lithium iron phosphate positive material recovery and reuse technology, can not only save money
Source reduces cost, and can protect environment.
Summary of the invention
The technical problem to be solved by the present invention is to solve to put existing for the regenerated lithium iron phosphate positive material of existing method
Capacitance is smaller, the larger technical problem of capacity attenuation rate, provides the titanium doped regeneration lithium iron phosphate positive material of one kind and its system
Preparation Method, application, to realize the extensive cycling and reutilization of positive material of waste lithium iron phosphate.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of preparation method of titanium doped regeneration lithium iron phosphate positive material, comprising the following steps:
S1: after lithium source, source of iron, titanium source, phosphorus source, carbon source is added in recycling lithium iron phosphate battery positive material, before obtaining
Body, the lithium source, source of iron, titanium source, the lithium in phosphorus source, iron, titanium, P elements molar ratio be 1:0.9-0.99:0.1-0.01:1,
The lithium source, source of iron, titanium source, phosphorus source, lithium, iron, titanium, phosphorus, carbon quality account for the percentage score of doped products quality in carbon source
It Wei not 0.5-1.5wt%, 0.06-0.1wt%, 0.5-1.25wt%, 1-2wt%, 3-20wt%；
S2: solvent medium is added in precursor, obtains intermediary after mixing；
S3: under an inert atmosphere, intermediary is handled by calcination, titanium doped regeneration lithium iron phosphate positive material is made.
Preferably, the lithium source, source of iron, titanium source, the lithium in phosphorus source, iron, titanium, P elements molar ratio be 1:x:(1-x):
1, x=0.9-0.99.
Preferably, the recycling lithium iron phosphate battery positive material obtains by the following method: will be from applying waste lithium ionic electricity
The positive plate separated in pond is heated under overheated steam, makes lithium iron phosphate battery positive material and plus plate current-collecting body point
From, then positive electrode obtained after drying, grinding, screening.
Preferably, the temperature of the overheated steam is 200-600 DEG C, and the screening was the screening of 200-500 mesh.
The major advantage of high-temperature steam heating are as follows: heated under 1. oxygen free conditions, keep raw material not oxidized to greatest extent.
2. heating under oxygen free condition, plus plate current-collecting body brittleness is good, and lithium iron phosphate battery positive material is easy to peel off.
Preferably, the lithium source is one or more of lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide or lithium oxalate.
Preferably, the source of iron is the one or more of ferric nitrate, ferrous acetate, ferrous oxalate or iron oxide.
Preferably, phosphorus source is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate or phosphoric acid.
Preferably, the titanium source is one or more of titanium dioxide, butyl titanate, titanium tetrachloride.
Preferably, the carbon source is one or more of starch, citric acid, sucrose, glucose or phenolic resin.
Preferably, the hybrid mode of the S2 step is ball milling, and the solvent medium is methanol, ethyl alcohol, isopropanol, acetone
Or the one or more of butanone, the mass ratio of the solvent medium and doped products are 1-2:1.
Preferably, the calcination temperature of the S3 step is 500-800 DEG C, calcination time 2-12h.
Preferably, the inert atmosphere of the S3 step is the gaseous mixture of argon gas, nitrogen or both.
The present invention also provides a kind of titanium doped regeneration lithium iron phosphate positive materials prepared by the above method.
The present invention also provides a kind of titanium doped regeneration lithium iron phosphate positive material by above method preparation is living as anode
Application of the property material in lithium ion battery.
The beneficial effects of the present invention are:
(1) titanium doped regeneration lithium iron phosphate positive material purity prepared by the present invention is very high, even particle distribution, is compacted close
Degree is high, by positive material of waste lithium iron phosphate regenerative process a step introduce element ti and improve the electricity of positive electrode
Chemical property, titanium doped regeneration lithium iron phosphate positive material obtained are applied in lithium ion battery as positive electrode active materials,
Compared with not used lithium iron phosphate positive material, there is excellent electro-chemical activity and cyclical stability.
(2) positive material of waste lithium iron phosphate regeneration technology of the present invention is simple, is easy to amplify, and is appropriate for waste phosphorus
The industrial scale reclaiming of sour lithium iron battery positive electrode.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is the 1 titanium doped regeneration lithium iron phosphate positive material of gained of embodiment and not used lithium iron phosphate positive material
XRD comparison diagram；
Fig. 2 is the SEM figure of the titanium doped regeneration lithium iron phosphate positive material of 2 gained of embodiment；
Fig. 3 is the 3 titanium doped regeneration lithium iron phosphate positive material of gained of embodiment and not used lithium iron phosphate positive material
0.1C rate charge-discharge curve comparison figure；
Fig. 4 is the 4 titanium doped regeneration lithium iron phosphate positive material of gained of embodiment and not used lithium iron phosphate positive material
1C circulation curve comparison figure.
Specific embodiment
In conjunction with the accompanying drawings, the present invention is further explained in detail.
Embodiment 1
The present embodiment provides a kind of preparation methods of titanium doped regeneration lithium iron phosphate positive material, comprising the following steps:
S1: after heating under 400 DEG C of overheated steams from the positive plate separated in waste and old lithium ion battery, make phosphorus
Sour lithium iron battery positive electrode is separated with plus plate current-collecting body, then by lithium iron phosphate battery positive material through drying, grinding, excessively 200
Recycling lithium iron phosphate battery positive material is obtained after mesh screening；
S2: lithium carbonate, ferric nitrate, butyl titanate, biphosphate is added in recycling lithium iron phosphate battery positive material
After ammonium, citric acid, obtain doped products, the lithium carbonate, ferric nitrate, butyl titanate, the lithium in ammonium dihydrogen phosphate, iron, titanium,
The molar ratio of P elements is 1:0.9:0.1:1, the lithium source, source of iron, titanium source, phosphorus source, lithium, iron, titanium, phosphorus, carbon in carbon source
The percentage that quality accounts for doped products quality is respectively 0.8wt%, 0.1wt%, 0.8wt%, 0.1wt%, 5wt%；
S3: being added acetone in doped products, and ball milling mixing is uniform, obtains a homogeneous mixture, and the acetone and doping produce
The mass ratio of object is 2:1；
S4: under high-purity argon gas protection, homogeneous mixture is calcined into 10h at 700 DEG C, titanium doped regeneration ferric phosphate is made
Lithium anode material.
The present embodiment is by titanium doped regeneration lithium iron phosphate positive material (LiFexTiyPO4/ C) and not used LiFePO4
Cell positive material (LiFePO4/ C) XRD spectrum compared (see Fig. 1), as can be seen from Figure 1, with not used phosphoric acid
Lithium iron battery positive electrode (LiFePO4/ C) it compares, titanium doped regeneration lithium iron phosphate positive material (LiFexTiyPO4/ C) knot
Structure does not change, and product purity is very high, and illustrating to adulterate does not influence the crystal structure of LiFePO4.
In addition, the present embodiment, which is also prepared for a kind of titanium doped regeneration lithium iron phosphate positive material of utilization, prepares button cell,
Steps are as follows:
The titanium doped regeneration lithium iron phosphate positive material of the present embodiment, conductive charcoal (carbon) black (Super P), PVDF is (poly-
Vinylidene) 85:10:5 in mass ratio ratio mixing, a certain amount of N-Methyl pyrrolidone (NMP) ball milling 1h afterwards, phase is added
Between viscosity that appropriate NMP adjusts slurry can be added to suitable coating, slurry is made；
The slurry made is coated uniformly on aluminium foil with spreader, with sheet-punching machine round pole piece is made after to be dried, it will
Pole piece 100 DEG C of freeze-day with constant temperature 12h in a vacuum drying oven, are made positive plate；
The assembly that button cell is carried out in the glove box full of dry argon gas, using metal lithium sheet as cathode, diaphragm is beauty
State Celgard 2400, electrolyte are 1.0mol/L LiPF6/EC+DMC+EMC (1:1:1, volume ratio), are assembled into button electricity
Pond.
By the button cell of preparation, related charge-discharge test is carried out, battery is charged to 3.8V with 0.2C constant current, then
0.2C constant current is put to 2.7V, cycle charge-discharge, and the gram volume of active material in iron electrode is calculated.Test result shows the button
Formula battery 0.2C discharge capacity is 151.2mAh/g, illustrates that titanium doped regeneration lithium iron phosphate positive material has excellent electrochemistry
Performance.
Button cell is prepared at room temperature 1C charge and discharge cycles 400 weeks using the present embodiment, capacity attenuation rate is 0.0186%/
Illustrate that titanium doped regeneration lithium iron phosphate positive material has excellent cycle performance in week.
Embodiment 2
The present embodiment provides a kind of preparation methods of titanium doped regeneration lithium iron phosphate positive material, comprising the following steps:
S1: after heating under 350 DEG C of overheated steams from the positive plate separated in waste and old lithium ion battery, make phosphorus
Sour lithium iron battery positive electrode is separated with plus plate current-collecting body, then by lithium iron phosphate battery positive material through drying, grinding, excessively 200
Recycling lithium iron phosphate battery positive material is obtained after mesh screening；
S2: lithium hydroxide, ferrous oxalate, titanium dioxide, phosphoric acid hydrogen is added in recycling lithium iron phosphate battery positive material
After diammonium, sucrose, obtain doped products, the lithium hydroxide, ferrous oxalate, titanium dioxide, the lithium in diammonium hydrogen phosphate, iron,
Titanium, P elements molar ratio be 1:0.98:0.02:1, the lithium source, source of iron, titanium source, phosphorus source, lithium, iron, titanium, phosphorus, carbon in carbon source
The percentage that element quality accounts for doped products quality is respectively 0.5wt%, 0.06wt%, 1.25wt%, 1.5wt%, 10wt%；
S3: being added isopropanol in doped products, and ball milling mixing is uniform, obtains a homogeneous mixture, the isopropanol with mix
The mass ratio of miscellaneous product is 1.5:1；
S4: under high pure nitrogen protection, homogeneous mixture is calcined into 8h at 650 DEG C, titanium doped regeneration ferric phosphate is made
Lithium anode material.
The SEM photograph of the titanium doped regeneration lithium iron phosphate positive material of the present embodiment is shown in Fig. 2, as can be seen from Figure 2, it can be seen that
The titanium doped regeneration lithium iron phosphate positive material of gained is mainly made of partial size in 200nm spherical particle below, particle
It is evenly distributed, compacted density is high.
In addition, the present embodiment is also prepared for a kind of button using the titanium doped regeneration lithium iron phosphate positive material of the present embodiment
Battery, step such as embodiment 1.
By the button cell of preparation, related charge-discharge test is carried out, battery is charged to 3.8V with 0.2C constant current, then
0.2C constant current is put to 2.7V, cycle charge-discharge, and the gram volume of active material in iron electrode is calculated.Test result shows the button
Formula battery 0.2C discharge capacity is 155.2mAh/g, illustrates that titanium doped regeneration lithium iron phosphate positive material has excellent electrochemistry
Performance.
Button cell is prepared at room temperature 1C charge and discharge cycles 400 weeks using the present embodiment, capacity attenuation rate is 0.0183%/
Illustrate that titanium doped regeneration lithium iron phosphate positive material has excellent cycle performance in week.
Embodiment 3
The present embodiment provides a kind of preparation methods of titanium doped regeneration lithium iron phosphate positive material, comprising the following steps:
S1: after heating under 600 DEG C of overheated steams from the positive plate separated in waste and old lithium ion battery, make phosphorus
Sour lithium iron battery positive electrode is separated with plus plate current-collecting body, then by lithium iron phosphate battery positive material through drying, grinding, excessively 500
Recycling lithium iron phosphate battery positive material is obtained after mesh screening；
S2: lithium oxalate, iron oxide, titanium tetrachloride, phosphoric acid, glucose is added in recycling lithium iron phosphate battery positive material
Afterwards, obtain doped products, the lithium oxalate, iron oxide, titanium tetrachloride, the lithium in phosphoric acid, iron, titanium, P elements molar ratio be
1:0.99:0.01:1, the lithium source, source of iron, titanium source, phosphorus source, lithium, iron, titanium, phosphorus, carbon quality account for doped products in carbon source
The percentage of quality is respectively 1wt%, 0.08wt%, 0.5wt%, 1wt%, 20wt%；
S3: being added dehydrated alcohol in doped products, and ball milling mixing is uniform, obtains a homogeneous mixture, the dehydrated alcohol
Mass ratio with doped products is 1:1；
S4: under high-purity argon gas protection, homogeneous mixture is calcined into 12h at 500 DEG C, titanium doped regeneration ferric phosphate is made
Lithium anode material.
In addition, the present embodiment is also prepared for a kind of button using the titanium doped regeneration lithium iron phosphate positive material of the present embodiment
Battery, step such as embodiment 1.
By the button cell of preparation, related charge-discharge test is carried out, battery is charged to 3.8V with 0.1C constant current, then
0.1C constant current is put to 2.7V, cycle charge-discharge, and the gram volume of active material in iron electrode is calculated.The present embodiment will also be titanium doped
Regenerate lithium iron phosphate positive material (LiFexTiyPO4/ C) and not used lithium iron phosphate battery positive material (LiFePO4/ C)
0.1C rate charge-discharge curve is compared (see Fig. 3), from figure 3, it can be seen that titanium doped regeneration lithium iron phosphate positive material
(LiFexTiyPO4/ C) and not used lithium iron phosphate battery positive material (LiFePO4/ C) preparation battery all have one it is bright
Aobvious discharge platform and a charging platform, discharge process is gentle, meets LiFePO4The feature of material.Simultaneously as it can be seen that being not used
Lithium iron phosphate battery positive material (LiFePO4/ C) discharge capacity be 132.9mAh/g, titanium doped regeneration LiFePO4 is just
Pole material (LiFexTiyPO4/ C) discharge capacity be 144.2mAh/g, illustrate titanium doped regeneration lithium iron phosphate positive material
(LiFexTiyPO4/ C) the positive discharge capacity of regeneration can be effectively improved.
Embodiment 4
The present embodiment provides a kind of preparation methods of titanium doped regeneration lithium iron phosphate positive material, comprising the following steps:
S1: after heating under 500 DEG C of overheated steams from the positive plate separated in waste and old lithium ion battery, make phosphorus
Sour lithium iron battery positive electrode is separated with plus plate current-collecting body, then by lithium iron phosphate battery positive material through drying, grinding, excessively 500
Recycling lithium iron phosphate battery positive material is obtained after mesh screening；
S2: lithium acetate, ferrous acetate, titanium dioxide, ammonium phosphate, phenol is added in recycling lithium iron phosphate battery positive material
After urea formaldehyde, obtain doped products, the lithium oxalate, ferric nitrate, titanium dioxide, the lithium in ammonium phosphate, iron, titanium, P elements
Molar ratio is 1:0.96:0.03:1, and the lithium source, source of iron, titanium source, phosphorus source, lithium, iron, titanium, phosphorus, carbon quality account in carbon source
The percentage of doped products quality is respectively 1.5wt%, 0.1wt%, 1.2wt%, 2wt%, 3wt%；
S3: being added butanone in doped products, and ball milling mixing is uniform, obtains a homogeneous mixture, and the butanone and doping produce
The mass ratio of object is 2:1；
S4: under high-purity argon gas protection, homogeneous mixture is calcined into 2h at 800 DEG C, titanium doped regeneration ferric phosphate is made
Lithium anode material.
In addition, the present embodiment is also prepared for a kind of button using the titanium doped regeneration lithium iron phosphate positive material of the present embodiment
Battery, step such as embodiment 1.
By the button cell of preparation, related charge-discharge test is carried out, battery is charged to 3.8V with 0.1C constant current, then
0.1C constant current is put to 2.7V, cycle charge-discharge, and the gram volume of active material in iron electrode is calculated.Test result shows the button
Formula battery 0.1C discharge capacity is 158.1mAh/g, illustrates that titanium doped regeneration lithium iron phosphate positive material has excellent electrochemistry
Performance.
The present embodiment is also by titanium doped regeneration lithium iron phosphate positive material (LiFexTiyPO4/ C) and not used ferric phosphate
Anode material of lithium battery (LiFePO4/ C) 1C circulation curve compared (see Fig. 4), as can be seen from Figure 4, using not
Lithium iron phosphate battery positive material (the LiFePO used4/ C) at room temperature 1C charge and discharge cycles 250 weeks, capacity attenuation rate is
0.0249%/week, and use titanium doped regeneration lithium iron phosphate battery positive material (LiFexTiyPO4/ C) in room temperature 1C charge and discharge
Circulation 400 weeks, capacity attenuation rate are 0.0196%/week, illustrate titanium doped regeneration lithium iron phosphate positive material (LiFexTiyPO4/
C the cyclical stability of regeneration anode) can be improved.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (10)
1. a kind of preparation method of titanium doped regeneration lithium iron phosphate positive material, which comprises the following steps:
S1: after lithium source, source of iron, titanium source, phosphorus source, carbon source is added in recycling lithium iron phosphate battery positive material, precursor is obtained, institute
State lithium source, source of iron, titanium source, lithium in phosphorus source, iron, titanium, P elements molar ratio be 1:0.9-0.99:0.1-0.01:1, the lithium
Source, source of iron, titanium source, phosphorus source, lithium, iron, titanium, phosphorus, carbon quality account for the percentage of doped products quality and are respectively in carbon source
0.5-1.5wt%, 0.06-0.1wt%, 0.5-1.25wt%, 1-2wt%, 3-20wt%；
S2: solvent medium is added in precursor, obtains intermediary after mixing；
S3: under an inert atmosphere, intermediary is handled by calcination, titanium doped regeneration lithium iron phosphate positive material is made.
2. the preparation method of titanium doped regeneration lithium iron phosphate positive material according to claim 1, which is characterized in that described
Lithium source, source of iron, titanium source, the lithium in phosphorus source, iron, titanium, P elements molar ratio be 1:x:(1-x): 1, wherein x=0.9-
0.99。
3. the preparation method of titanium doped regeneration lithium iron phosphate positive material according to claim 1 or 2, which is characterized in that
The recycling lithium iron phosphate battery positive material obtains by the following method: will separate just from waste and old lithium ion battery
Pole piece is heated under overheated steam, separates lithium iron phosphate battery positive material with plus plate current-collecting body, then positive electrode is passed through
It is obtained after dry, grinding, screening.
4. the preparation method of titanium doped regeneration lithium iron phosphate positive material according to claim 3, which is characterized in that described
The temperature of overheated steam is 200-600 DEG C, and the screening was the screening of 200-500 mesh.
5. the preparation method of titanium doped regeneration lithium iron phosphate positive material according to claim 1-4, feature
It is, the lithium source is one or more of lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide or lithium oxalate, and the source of iron is
The one or more of ferric nitrate, ferrous acetate, ferrous oxalate or iron oxide, phosphorus source be ammonium dihydrogen phosphate, diammonium hydrogen phosphate,
One or more of ammonium phosphate or phosphoric acid, the titanium source be one of titanium dioxide, butyl titanate, titanium tetrachloride or
Several, the carbon source is one or more of starch, citric acid, sucrose, glucose or phenolic resin.
6. the preparation method of titanium doped regeneration lithium iron phosphate positive material according to claim 1-5, feature
It is, the hybrid mode of the S2 step is ball milling, and the solvent medium is the one of methanol, ethyl alcohol, isopropanol, acetone or butanone
Kind is several, and the mass ratio of the solvent medium and doped products is 1-2:1.
7. the preparation method of titanium doped regeneration lithium iron phosphate positive material according to claim 1-6, feature
It is, the calcination temperature of the S3 step is 500-800 DEG C, calcination time 2-12h.
8. the preparation method of titanium doped regeneration lithium iron phosphate positive material according to claim 1-7, feature
It is, the inert atmosphere of the S3 step is the gaseous mixture of argon gas, nitrogen or both.
9. a kind of titanium doped regeneration lithium iron phosphate positive material prepared by the method by any one of claim 1-8.
10. a kind of titanium doped regeneration lithium iron phosphate positive material as claimed in claim 9 is as positive electrode active materials in lithium ion
Application in battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810952828.5A CN109167119A (en) | 2018-08-21 | 2018-08-21 | Titanium doped regeneration lithium iron phosphate positive material of one kind and preparation method thereof, application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810952828.5A CN109167119A (en) | 2018-08-21 | 2018-08-21 | Titanium doped regeneration lithium iron phosphate positive material of one kind and preparation method thereof, application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109167119A true CN109167119A (en) | 2019-01-08 |
Family
ID=64896207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810952828.5A Pending CN109167119A (en) | 2018-08-21 | 2018-08-21 | Titanium doped regeneration lithium iron phosphate positive material of one kind and preparation method thereof, application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109167119A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110098442A (en) * | 2019-03-11 | 2019-08-06 | 昆明理工大学 | A method of LiFePO4 is regenerated using leaching-spray drying-solid phase method |
| CN110620278A (en) * | 2019-09-25 | 2019-12-27 | 深圳清华大学研究院 | Method for recovering anode material of waste lithium iron phosphate battery |
| CN112952097A (en) * | 2021-02-23 | 2021-06-11 | 贵州安达科技能源股份有限公司 | Lithium iron phosphate anode material and preparation method and application thereof |
| WO2021114747A1 (en) * | 2019-12-09 | 2021-06-17 | 贝特瑞（天津）纳米材料制造有限公司 | Method for selective oxidation-reduction regeneration from waste lithium iron phosphate, regenerated lithium iron phosphate, and lithium ion battery |
| CN113097455A (en) * | 2021-02-23 | 2021-07-09 | 雅安锂盛新能企业管理中心(有限合伙) | Modified lithium iron phosphate composite material, positive electrode material and preparation method thereof |
| CN114583313A (en) * | 2022-03-11 | 2022-06-03 | 江苏协鑫锂电科技有限公司 | Method for recycling waste phosphate positive electrode material |
| CN114804054A (en) * | 2022-05-09 | 2022-07-29 | 广东工业大学 | Carbon-coated lithium ferric manganese phosphate cathode material and preparation method thereof |
| CN115849326A (en) * | 2022-12-15 | 2023-03-28 | 楚能新能源股份有限公司 | Preparation method of Ti-doped lithium iron phosphate anode material, anode material and application |
| CN115974041A (en) * | 2023-03-07 | 2023-04-18 | 锂白新材料科技(江苏)有限公司 | Lithium iron phosphate cathode material and preparation method and application thereof |
| CN116216686A (en) * | 2023-03-28 | 2023-06-06 | 陕西创普斯新能源科技有限公司 | Preparation method of lithium iron phosphate anode material |
| CN116395658A (en) * | 2023-03-28 | 2023-07-07 | 陕西创普斯新能源科技有限公司 | Preparation method of titanium-doped lithium iron phosphate material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106602060A (en) * | 2016-12-26 | 2017-04-26 | 贝特瑞（天津）纳米材料制造有限公司 | Low-cost lithium iron phosphate material, and preparation method and application thereof |
| CN108376768A (en) * | 2018-01-29 | 2018-08-07 | 国网河南省电力公司电力科学研究院 | A kind of additive Mn regeneration lithium iron phosphate positive material and preparation method thereof |
-
2018
- 2018-08-21 CN CN201810952828.5A patent/CN109167119A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106602060A (en) * | 2016-12-26 | 2017-04-26 | 贝特瑞（天津）纳米材料制造有限公司 | Low-cost lithium iron phosphate material, and preparation method and application thereof |
| CN108376768A (en) * | 2018-01-29 | 2018-08-07 | 国网河南省电力公司电力科学研究院 | A kind of additive Mn regeneration lithium iron phosphate positive material and preparation method thereof |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110098442A (en) * | 2019-03-11 | 2019-08-06 | 昆明理工大学 | A method of LiFePO4 is regenerated using leaching-spray drying-solid phase method |
| CN110620278B (en) * | 2019-09-25 | 2021-07-02 | 深圳清华大学研究院 | Method for recovering anode material of waste lithium iron phosphate battery |
| CN110620278A (en) * | 2019-09-25 | 2019-12-27 | 深圳清华大学研究院 | Method for recovering anode material of waste lithium iron phosphate battery |
| JP7161606B2 (en) | 2019-12-09 | 2022-10-26 | ビーティーアール（ティアンジン） ナノ マテリアル マニュファクチャー カンパニー，リミテッド | Method for Selective Redox Regeneration of Waste Lithium Iron Phosphate, Regenerated Lithium Iron Phosphate and Lithium Ion Battery |
| CN113036253B (en) * | 2019-12-09 | 2023-01-13 | 锂源(深圳)科学研究有限公司 | Method for selective oxidation-reduction regeneration of waste lithium iron phosphate, regenerated lithium iron phosphate and lithium ion battery |
| WO2021114747A1 (en) * | 2019-12-09 | 2021-06-17 | 贝特瑞（天津）纳米材料制造有限公司 | Method for selective oxidation-reduction regeneration from waste lithium iron phosphate, regenerated lithium iron phosphate, and lithium ion battery |
| JP2022517160A (en) * | 2019-12-09 | 2022-03-07 | ビーティーアール（ティアンジン） ナノ マテリアル マニュファクチャー カンパニー，リミテッド | Selective redox regeneration method for waste lithium iron phosphate, regenerated lithium iron phosphate and lithium-ion batteries |
| US12021206B2 (en) | 2019-12-09 | 2024-06-25 | Liyuan (Shenzhen) Scientific Research Co., Ltd. | Method for recycling waste lithium iron phosphate by selective oxidation-reduction, recycled lithium iron phosphate, and lithium ion battery |
| CN113036253A (en) * | 2019-12-09 | 2021-06-25 | 贝特瑞（天津）纳米材料制造有限公司 | Method for selective oxidation-reduction regeneration of waste lithium iron phosphate, regenerated lithium iron phosphate and lithium ion battery |
| CN113097455A (en) * | 2021-02-23 | 2021-07-09 | 雅安锂盛新能企业管理中心(有限合伙) | Modified lithium iron phosphate composite material, positive electrode material and preparation method thereof |
| CN112952097A (en) * | 2021-02-23 | 2021-06-11 | 贵州安达科技能源股份有限公司 | Lithium iron phosphate anode material and preparation method and application thereof |
| CN114583313B (en) * | 2022-03-11 | 2024-02-20 | 江苏协鑫锂电科技有限公司 | Method for recycling waste phosphate cathode material |
| CN114583313A (en) * | 2022-03-11 | 2022-06-03 | 江苏协鑫锂电科技有限公司 | Method for recycling waste phosphate positive electrode material |
| CN114804054A (en) * | 2022-05-09 | 2022-07-29 | 广东工业大学 | Carbon-coated lithium ferric manganese phosphate cathode material and preparation method thereof |
| CN115849326A (en) * | 2022-12-15 | 2023-03-28 | 楚能新能源股份有限公司 | Preparation method of Ti-doped lithium iron phosphate anode material, anode material and application |
| CN115849326B (en) * | 2022-12-15 | 2024-02-27 | 楚能新能源股份有限公司 | Preparation method of Ti-doped lithium iron phosphate positive electrode material, positive electrode material and application |
| CN115974041A (en) * | 2023-03-07 | 2023-04-18 | 锂白新材料科技(江苏)有限公司 | Lithium iron phosphate cathode material and preparation method and application thereof |
| CN116216686A (en) * | 2023-03-28 | 2023-06-06 | 陕西创普斯新能源科技有限公司 | Preparation method of lithium iron phosphate anode material |
| CN116395658A (en) * | 2023-03-28 | 2023-07-07 | 陕西创普斯新能源科技有限公司 | Preparation method of titanium-doped lithium iron phosphate material |
| CN116216686B (en) * | 2023-03-28 | 2024-04-19 | 陕西创普斯新能源科技有限公司 | Preparation method of lithium iron phosphate anode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109167119A (en) | Titanium doped regeneration lithium iron phosphate positive material of one kind and preparation method thereof, application | |
| CN102751548B (en) | Method for recovering and preparing lithium iron phosphate from waste lithium iron phosphate battery | |
| US20200328406A1 (en) | Layered lithium-rich manganese-based cathode material with olivine structured limpo4 surface modification and preparation method thereof | |
| CN104201323B (en) | The preparation method of alumina-coated lithium cobaltate cathode material | |
| CN110474044A (en) | A kind of high-performance water system Zinc ion battery positive electrode and the preparation method and application thereof | |
| CN107437617B (en) | A kind of surface modification method, gained richness lithium material and application improving rich lithium material chemical property | |
| CN108899531A (en) | A kind of preparation method of Phosphate coating nickel cobalt aluminium tertiary cathode material | |
| CN110350198B (en) | Preparation method of sodium phosphate surface modified sodium ion battery positive electrode material | |
| WO2011009231A1 (en) | Method for preparing carbon-coated positive material of lithium ion battery | |
| CN108933237B (en) | Preparation method and application of lithium ion battery positive electrode material | |
| CN107093739B (en) | Potassium manganese oxide for potassium ion battery anode material and preparation method thereof | |
| CN111082009B (en) | Lithium-rich manganese-based composite positive electrode material improved by adopting phosphate and preparation method thereof | |
| WO2020259436A1 (en) | Method for improving stability and processability of ternary positive electrode material | |
| CN105789606A (en) | Preparation method of lithium titanate coated lithium ion battery nickel cobalt manganese cathode material | |
| WO2016176928A1 (en) | Negative electrode material, preparation method therefor, and lithium-ion secondary battery using the negative electrode material | |
| CN102299303A (en) | Method for preparing lithium iron phosphate-lithium vanadium phosphate cathode material of lithium ion battery | |
| CN109244395B (en) | Preparation method of in-situ nitrogen-doped carbon-coated lithium iron phosphate positive electrode material | |
| CN107895778A (en) | A kind of nitrogen sulphur codope carbon surface modification lithium iron phosphate positive material, preparation method and the usage | |
| CN113764762A (en) | Method for synthesizing high-performance lithium ion battery anode material by using waste lithium ion battery | |
| CN115010107A (en) | Method for preparing lithium iron manganese phosphate cathode material from phosphorized slag | |
| CN113571691B (en) | Zirconium-nitrogen co-doped carbon point modified single crystal ternary positive electrode material and preparation method thereof | |
| CN104347852A (en) | Preparation method of lithium manganese phosphate-lithium vanadium phosphate composite material | |
| CN108520946B (en) | Magnesium-iron hydride-graphite composite electrode material and preparation method and application thereof | |
| CN104934585B (en) | A kind of vanadium based compound Zn3V3O8And its preparation method and application | |
| CN110085862A (en) | A kind of sode cell electrode material Na1+xFexTi2-x(PO4)3And its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190108 |