CN109599559A - A kind of spherical lithium ferric phosphate composite positive pole material and preparation method - Google Patents
A kind of spherical lithium ferric phosphate composite positive pole material and preparation method Download PDFInfo
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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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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
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- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- C01G45/12—Manganates manganites or permanganates
- C01G45/1207—Permanganates ([MnO]4-) or manganates ([MnO4]2-)
- C01G45/1214—Permanganates ([MnO]4-) or manganates ([MnO4]2-) containing alkali metals
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- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/11—Powder tap density
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of spherical lithium ferric phosphate composite positive pole material and preparation methods.The lithium iron phosphate positive material is made by following steps: solvent a, is added in lithium source, phosphorus source, source of iron, tartaric acid, micropore spherical shape substrate is then added, in the reaction vessel heating reaction, washs, separate, it is dry, and spherical LiFePO 4 composite precursor is made；B, presoma is subjected to step-up temperature calcining under nitrogen atmosphere, spherical lithium ferric phosphate composite positive pole material is made.The method has the advantages that the spherical of rule is presented in positive electrode material precursor particle prepared by the present invention, crystal property is good, the spherical macro lithium iron phosphate positive material tap density of acquisition is big, specific capacity is high, high rate performance is excellent, and preparation process is simple, and low energy consumption, it is at low cost, it is suitble to large-scale production.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular to the preparation of positive electrode, more particularly, to a kind of spherical phosphorus
Sour iron lithium composite positive pole and preparation method.
Background technique
Lithium ion battery is new generation of green high capacity power source, since its nineteen ninety emerges, has just had specific energy high, has followed
The advantages that ring service life is long, memory-less effect, and self discharge is small and operating temperature range is wide, has been widely used in a variety of portable
On the mobile power source and small-sized electric tool of formula electronic product.The main composition material of lithium ion battery includes electrolyte, isolation
Material, positive and negative pole material etc..Positive electrode occupies larger proportion, and performance directly affects the performance of lithium ion battery, at
This also directly determines battery cost height.
For LiFePO4 using iron, phosphorus as raw material, abundance is cheap, it is considered to be power lithium-ion battery is preferred
Positive electrode.3.2 ~ 3 .3V of LiFePO4 discharge platform is lower than cobalt acid lithium, 3.6 ~ 3 .7V of LiMn2O4, but its discharge platform is more
Steadily；LiFePO4 has excellent heavy-current discharge characteristic, can bear the continuous discharge of 7C and sparking for 20C or more.
LiFePO4 determines that it is used in power with its characteristic in terms of price, safety, thermal stability and big multiplying power discharging
Field of lithium ion battery has incomparable advantage, there is the great market space.Currently, the synthesis of LiFePO4 still with
Based on synthesis in solid state.I.e. by source of iron, phosphorus source, lithium source ground and mixed together, then high-temperature calcination under inert gas protection again
Synthesis.
Number of patent application 201810069539.0 discloses a kind of preparation method of lithium iron phosphate positive material, this method packet
Containing following steps: (1) prepared by slurry: molysite, microcosmic salt being added in aqueous slkali, heating reaction obtains ferrophosphorus compound pulp；
(2) wet ball grinding: being added doping vario-property agent, carbon source and lithium salts in the slurry, and wet ball grinding to granularity is 50 ~ 150nm；(3) it sprays
Mist is granulated: by the slurry mist projection granulating after ball milling, obtaining spherical precursor；(4) high temperature sintering: by spherical precursor in inert atmosphere
Lower sintering, obtains lithium iron phosphate positive material after being cooled to room temperature.
Number of patent application 201711107890.6 discloses a kind of lithium iron phosphate positive material and preparation method thereof, belongs to lithium
Battery technology field.Its prepare include in material 30 ~ 70 parts of 20 ~ 40 parts of lithium hydroxide, microcrystalline cellulose by weight,
30 ~ 40 parts of water, 90 ~ 150 parts of ferric phosphate are by raw material reaction, prepare slurry, drying, sintering step and then be prepared.
Number of patent application 201810001224.2 discloses a kind of preparation method of spherical lithium ferric phosphate composite positive pole material.
The following steps are included: lithium source, carbon source, ferric phosphate and additive are added to the water it is uniformly mixed, then to mixing gained slurry carry out
Then grinding is sintered with air-stream spraying drying equipment to the slurry mist projection granulating after grinding, then by mist projection granulating resulting material, burn
Spherical lithium ferric phosphate composite positive pole material is obtained after the completion of knot.
Number of patent application 201810054891.7 discloses a kind of preparation method of lithium iron phosphate positive material, and this method is first
Phenols/ferric lithium phosphate precursor mixed liquor is configured, then adds aldehydes solution, carries out phenolic aldehyde contracting under the conditions of autoclave later
The hydro-thermal reaction of conjunction obtains the first clad of LiFePO4 of phenolic resin formation, coats polyvinyl pyrrole on its surface later
Alkanone obtains the second clad, and lithium iron phosphate positive material finally is prepared by spray drying, sintering.
It can be seen that being used for the iron lithium phosphate positive electrode of lithium ion battery in the prior art, there are Granularity Distributions
Range is wide, and crystal particle diameter is big, and powder is random particle, and bulk density is low, and general tap density only has 1.0g/cm3, it is far below
Cobalt acid lithium (2.8g/cm at present3), LiMn2O4 (2.4g/cm3), ternary material (2.2g/cm3)) tap density, low accumulation
Density makes the volume capacity of LiFePO4 more much lower than other lithium ion anode materials, hinders the material in dynamic lithium battery
The application in field.
Summary of the invention
Effectively to solve above-mentioned technical problem, the invention proposes a kind of spherical lithium ferric phosphate composite positive pole material and preparations
Method can be effectively improved the shape characteristic of iron lithium phosphate positive electrode, and tap density is high, has excellent performance.
The specific technical solution of the present invention is as follows:
A kind of preparation method of spherical lithium ferric phosphate composite positive pole material, the spherical lithium ferric phosphate composite positive pole material are by lithium
Source, phosphorus source and source of iron in the presence of tartaric acid, be added micropore spherical shape substrate react obtained spherical LiFePO 4 it is compound before
Body is driven, then ball milling simultaneously calcine and be made, specific preparation step by step-up temperature are as follows:
A, lithium source, phosphorus source and source of iron are mixed, is dissolved mixture using solvent, lithium source, phosphorus source and source of iron total weight is added
Then 40% crystal growth inhibitor tartaric acid is added micropore spherical shape substrate, is transferred to the reaction vessel of polytetrafluoroethylene (PTFE) material
In, 220 ~ 250 DEG C of 1 ~ 3h of reaction are heated to, are cooled down after reaction, then with deionized water and ethanol washing, be centrifuged,
It is dry, spherical LiFePO 4 composite precursor is made；
B, by spherical LiFePO 4 composite precursor ball milling made from step a, step-up temperature calcining, system are carried out under nitrogen atmosphere
Obtain spherical lithium ferric phosphate composite positive pole material.
Preferably, in the step a, lithium source is at least one of lithium hydroxide, lithium dihydrogen phosphate, two lithium of phosphoric acid hydrogen.
Preferably, in the step a, phosphorus source is at least one of phosphoric acid, ferric phosphate, lithium phosphate.
Preferably, in the step a, source of iron is at least one of ferric acetate, ferric phosphate, ferrous phosphate.
Preferably, in the step a, lithium source, source of iron, the molar ratio of substance in phosphorus source are Li:Fe:P=1 ~ 3:1:1.
Preferably, in the step a, solvent is one of ethyl alcohol, butanol.
Preferably, in step a, micropore spherical shape substrate be partial size be 2-10 microns spherical micropore cobalt acid lithium, LiMn2O4, nickel
At least one of sour lithium, nickle cobalt lithium manganate.
Preferably, in the step a, the mass ratio of micropore spherical shape substrate is in spherical LiFePO 4 composite precursor
10%。
Preferably, in the step b, the mode of step-up temperature calcining is 2h first to be calcined at 400 DEG C, then at 650 DEG C
Lower calcining 2h finally calcines 10 ~ 15h at 770 DEG C；The heating rate is 4 DEG C/min.
The present invention utilizes hydro-thermal method, prepares LiFePO4 composite precursor at a lower temperature, in the short time.Meanwhile
Preparation process is added crystal growth inhibitor and combines, and a large amount of uses of crystal growth inhibitor cause LiFePO4 in micropore
It is grown to tiny crystal grains in the mesh of spherical substrate, and is compounded to form spherical knot by way of micropore spherical shape substrate self assembly
Structure.Simple process, low energy consumption, excellent product performance, spherical easily-controllable.
Above content of the present invention also proposes a kind of spherical lithium ferric phosphate composite positive pole material, is made by following steps: a, general
Solvent is added in lithium source, phosphorus source, source of iron, tartaric acid, and micropore spherical shape substrate is then added, in the reaction vessel heating reaction, washing,
Separation, it is dry, spherical LiFePO 4 composite precursor is made；B, by presoma ball milling, step-up temperature is carried out under nitrogen atmosphere
Calcining to get.
The invention has the benefit that
1. proposing the method for preparing spherical lithium ferric phosphate composite positive pole material using hydrothermal reaction at low temperature.
2. the spherical of rule is presented in positive electrode material precursor particle prepared by the present invention, assembled by small grains, is tied
Brilliant performance is good, and the spherical macro tap density of acquisition is big, and specific capacity is high, and high rate performance is excellent.
3. preparation process of the invention is simple, low energy consumption, at low cost, is suitble to large-scale production.
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
A, lithium source, phosphorus source and source of iron are mixed, is dissolved mixture using solvent, lithium source, phosphorus source and source of iron total weight is added
Then 40% crystal growth inhibitor tartaric acid is added micropore spherical shape substrate, is transferred to the reaction vessel of polytetrafluoroethylene (PTFE) material
In, 235 DEG C of reaction 2h are heated to, are cooled down after reaction, then with deionized water and ethanol washing, is centrifuged, dries, are made
Obtain spherical LiFePO 4 composite precursor；Wherein, lithium source is lithium hydroxide, and phosphorus source is phosphoric acid, and source of iron is ferric acetate, and solvent is second
Alcohol；Lithium source, phosphorus source, the molar ratio of substance in source of iron are Li:Fe:P=2:1:1；Micropore spherical shape substrate is that partial size is 2-10 microns
Spherical micropore cobalt acid lithium；The mass ratio of micropore spherical shape substrate is 10% in spherical LiFePO 4 composite precursor；
B, by spherical LiFePO 4 composite precursor ball milling made from step a, step-up temperature calcining, rank are carried out under nitrogen atmosphere
The mode of Duan Shengwen calcining is first to calcine 2h at 400 DEG C, 2h is then calcined at 650 DEG C, is finally calcined at 770 DEG C
12h, heating rate are 4 DEG C/min, and spherical lithium ferric phosphate composite positive pole material is made.
Embodiment 2
A, lithium source, phosphorus source and source of iron are mixed, is dissolved mixture using solvent, lithium source, phosphorus source and source of iron total weight is added
Then 40% crystal growth inhibitor tartaric acid is added micropore spherical shape substrate, is transferred to the reaction vessel of polytetrafluoroethylene (PTFE) material
In, 220 DEG C of reaction 3h are heated to, are cooled down after reaction, then with deionized water and ethanol washing, is centrifuged, dries, are made
Obtain spherical LiFePO 4 composite precursor；Wherein, lithium source is lithium dihydrogen phosphate, and phosphorus source is ferric phosphate, and source of iron is ferric phosphate, solvent
For butanol；Lithium source, phosphorus source, the molar ratio of substance in source of iron are Li:Fe:P=1:1:1；It is 2-10 that micropore spherical shape substrate, which is partial size,
The spherical micropore LiMn2O4 of micron；The mass ratio of micropore spherical shape substrate is 10% in spherical LiFePO 4 composite precursor；
B, spherical LiFePO 4 composite precursor ball milling made from step a is scatter, carries out step-up temperature under nitrogen atmosphere
The mode of calcining, step-up temperature calcining is first to calcine 2h at 400 DEG C, 2h is then calcined at 650 DEG C, finally at 770 DEG C
10h is calcined, heating rate is 4 DEG C/min, and spherical lithium ferric phosphate composite positive pole material is made.
Embodiment 3
A, lithium source, phosphorus source and source of iron are mixed, is dissolved mixture using solvent, lithium source, phosphorus source and source of iron total weight is added
Then 40% crystal growth inhibitor tartaric acid is added micropore spherical shape substrate, is transferred to the reaction vessel of polytetrafluoroethylene (PTFE) material
In, 250 DEG C of reaction 1h are heated to, are cooled down after reaction, then with deionized water and ethanol washing, is centrifuged, dries, are made
Obtain spherical LiFePO 4 composite precursor；Wherein, lithium source is two lithium of phosphoric acid hydrogen, and phosphorus source is lithium phosphate, and source of iron is ferrous phosphate, molten
Agent is ethyl alcohol；Lithium source, phosphorus source, the molar ratio of substance in source of iron are Li:Fe:P=3:1:1；It is 2- that micropore spherical shape substrate, which is partial size,
10 microns of spherical micropore lithium nickelate；The mass ratio of micropore spherical shape substrate is 10% in spherical LiFePO 4 composite precursor；
B, by spherical LiFePO 4 composite precursor ball milling made from step a, step-up temperature calcining, rank are carried out under nitrogen atmosphere
The mode of Duan Shengwen calcining is first to calcine 2h at 400 DEG C, 2h is then calcined at 650 DEG C, is finally calcined at 770 DEG C
15h, heating rate are 4 DEG C/min, and spherical lithium ferric phosphate composite positive pole material is made.
Embodiment 4
A, lithium source, phosphorus source and source of iron are mixed, is dissolved mixture using solvent, lithium source, phosphorus source and source of iron total weight is added
Then 40% crystal growth inhibitor tartaric acid is added micropore spherical shape substrate, is transferred to the reaction vessel of polytetrafluoroethylene (PTFE) material
In, 230 DEG C of reaction 2.5h are heated to, are cooled down after reaction, then with deionized water and ethanol washing, is centrifuged, dries,
Spherical LiFePO 4 composite precursor is made；Wherein, lithium source is lithium hydroxide, and phosphorus source is phosphoric acid, and source of iron is ferric acetate, and solvent is
Butanol；Lithium source, phosphorus source, the molar ratio of substance in source of iron are Li:Fe:P=1:1:1；Micropore spherical shape substrate is that partial size is 2-10 micro-
The spherical micropore nickle cobalt lithium manganate of rice；The mass ratio of micropore spherical shape substrate is 10% in spherical LiFePO 4 composite precursor；
B, by spherical LiFePO 4 composite precursor ball milling made from step a, step-up temperature calcining, rank are carried out under nitrogen atmosphere
The mode of Duan Shengwen calcining is first to calcine 2h at 400 DEG C, 2h is then calcined at 650 DEG C, is finally calcined at 770 DEG C
11h, heating rate are 4 DEG C/min, and spherical lithium ferric phosphate composite positive pole material is made.
Embodiment 5
A, lithium source, phosphorus source and source of iron are mixed, is dissolved mixture using solvent, lithium source, phosphorus source and source of iron total weight is added
Then 40% crystal growth inhibitor tartaric acid is added micropore spherical shape substrate, is transferred to the reaction vessel of polytetrafluoroethylene (PTFE) material
In, 240 DEG C of reaction 1.5h are heated to, are cooled down after reaction, then with deionized water and ethanol washing, is centrifuged, dries,
Spherical LiFePO 4 composite precursor is made；Wherein, lithium source is lithium dihydrogen phosphate, and phosphorus source is lithium phosphate, and source of iron is ferrous phosphate,
Solvent is butanol；Lithium source, phosphorus source, the molar ratio of substance in source of iron are Li:Fe:P=3:1:1；Micropore spherical shape substrate is that partial size is
2-10 microns of spherical micropore cobalt acid lithium；The mass ratio of micropore spherical shape substrate is 10% in spherical LiFePO 4 composite precursor；
B, by spherical LiFePO 4 composite precursor ball milling made from step a, step-up temperature calcining, rank are carried out under nitrogen atmosphere
The mode of Duan Shengwen calcining is first to calcine 2h at 400 DEG C, 2h is then calcined at 650 DEG C, is finally calcined at 770 DEG C
14h, heating rate are 4 DEG C/min, and spherical lithium ferric phosphate composite positive pole material is made.
Comparative example 1
A, lithium source, phosphorus source and source of iron are mixed, is dissolved mixture using solvent, the reaction for being transferred to polytetrafluoroethylene (PTFE) material is held
In device, 240 DEG C of reaction 1.5h are heated to, are cooled down after reaction, then with deionized water and ethanol washing, is centrifuged, does
It is dry, LiFePO4 composite precursor is made；Wherein, lithium source is lithium dihydrogen phosphate, and phosphorus source is lithium phosphate, and source of iron is ferrous phosphate,
Solvent is butanol；Lithium source, phosphorus source, the molar ratio of substance in source of iron are Li:Fe:P=3:1:1；
B, by LiFePO4 composite precursor ball milling made from step a, step-up temperature calcining, stage liter are carried out under nitrogen atmosphere
The mode of temperature calcining is first to calcine 2h at 400 DEG C, 2h is then calcined at 650 DEG C, 14h is finally calcined at 770 DEG C, is risen
Warm speed is 4 DEG C/min, and iron phosphate compound anode material of lithium is made.
Comparative example 1 is not raw using tartaric acid inhibition crystal grain using lithium source, phosphorus source and source of iron are mounted in micropore spherical shape substrate in advance
It grows and forms fine-grain assembling in micropore, obtained LiFePO4 CRYSTALLITE SIZES is uneven and in irregular shape, and sphericity is poor, shadow
Ring service performance.
Iron phosphate compound anode material of lithium made from above-described embodiment 1 ~ 5 and comparative example 1, tests its shape characteristic, partial size
Range, sphericity and tap density, method or the condition for testing characterization are as follows:
Shape characteristic: taking 1g positive electrode produced by the present invention, is tested using SEM scarnning mirror, observes positive electrode in SEM photograph
Shape characteristic.
Particle size range, sphericity: 1g positive electrode produced by the present invention is taken, is tested, is obtained using laser particle analyzer
The particle size distribution range and average spherical degree of positive electrode.
Tap density: taking 1g positive electrode produced by the present invention, is surveyed using powder JZ-7 type tap density tester
Examination, obtains the tap density of positive electrode.
The results are shown in Table 1.
Table 1:
Claims (10)
1. a kind of preparation method of spherical lithium ferric phosphate composite positive pole material, it is characterised in that: the spherical LiFePO 4 is compound
Positive electrode is that micropore spherical shape substrate is added in the presence of tartaric acid by lithium source, phosphorus source and source of iron, react that spherical shape is made
LiFePO4 composite precursor, then ball milling simultaneously calcine and be made, specific preparation step by step-up temperature are as follows:
A, lithium source, phosphorus source and source of iron are mixed, is dissolved mixture using solvent, lithium source, phosphorus source and source of iron total weight is added
Then 40% crystal growth inhibitor tartaric acid is added micropore spherical shape substrate, is transferred to the reaction vessel of polytetrafluoroethylene (PTFE) material
In, 220 ~ 250 DEG C of 1 ~ 3h of reaction are heated to, are cooled down after reaction, then with deionized water and ethanol washing, be centrifuged,
It is dry, spherical LiFePO 4 composite precursor is made；
B, by spherical LiFePO 4 composite precursor ball milling made from step a, step-up temperature calcining, system are carried out under nitrogen atmosphere
Obtain spherical lithium ferric phosphate composite positive pole material.
2. a kind of preparation method of spherical lithium ferric phosphate composite positive pole material according to claim 1, it is characterised in that: described
In step a, lithium source is at least one of lithium hydroxide, lithium dihydrogen phosphate, two lithium of phosphoric acid hydrogen.
3. a kind of preparation method of spherical lithium ferric phosphate composite positive pole material according to claim 1, it is characterised in that: described
In step a, phosphorus source is at least one of phosphoric acid, ferric phosphate, lithium phosphate.
4. a kind of preparation method of spherical lithium ferric phosphate composite positive pole material according to claim 1, it is characterised in that: described
In step a, source of iron is at least one of ferric acetate, ferric phosphate, ferrous phosphate.
5. a kind of preparation method of spherical lithium ferric phosphate composite positive pole material according to claim 1, it is characterised in that: described
In step a, lithium source, source of iron, the molar ratio of substance in phosphorus source are Li:Fe:P=1 ~ 3:1:1.
6. a kind of preparation method of spherical lithium ferric phosphate composite positive pole material according to claim 1, it is characterised in that: described
In step a, solvent is one of ethyl alcohol, butanol.
7. a kind of preparation method of spherical lithium ferric phosphate composite positive pole material according to claim 1, it is characterised in that: described
In step a, micropore spherical shape substrate be partial size be 2-10 microns spherical micropore cobalt acid lithium, LiMn2O4, lithium nickelate, nickle cobalt lithium manganate
At least one of.
8. a kind of preparation method of spherical lithium ferric phosphate composite positive pole material according to claim 1, it is characterised in that: described
In step a, the mass ratio of micropore spherical shape substrate is 10% in spherical LiFePO 4 composite precursor.
9. a kind of preparation method of spherical lithium ferric phosphate composite positive pole material according to claim 1, it is characterised in that: described
In step b, the mode of step-up temperature calcining is first to calcine 2h at 400 DEG C, 2h is then calcined at 650 DEG C, finally 770
10 ~ 15h is calcined at DEG C；The heating rate is 4 DEG C/min.
10. a kind of spherical lithium ferric phosphate composite positive pole material that any one of claim 1 ~ 9 the method is prepared.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114348985A (en) * | 2021-12-31 | 2022-04-15 | 江苏贝特瑞纳米科技有限公司 | High-compaction phosphate type cathode material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114348985A (en) * | 2021-12-31 | 2022-04-15 | 江苏贝特瑞纳米科技有限公司 | High-compaction phosphate type cathode material |
| CN114348985B (en) * | 2021-12-31 | 2023-08-11 | 江苏贝特瑞纳米科技有限公司 | High-compaction phosphate type positive electrode material |
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