CN102104148A - Mixed rare earth compound-doped and modified lithium iron phosphate cathode material and preparation method thereof - Google Patents
Mixed rare earth compound-doped and modified lithium iron phosphate cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a mixed rare earth compound-doped and modified lithium iron phosphate cathode material and a preparation method thereof, and belongs to the technical field of preparation of electrochemical power materials. In the cathode material, Fe-site doping is performed on a LiFePO4 cathode material by at least one rare earth element in a mixed rare earth compound; and the LiFePO4 cathode material is doped and modified by utilizing the mixed rare earth compound with low price by a solid-phase synthesis method. The process comprises the following steps of: adding a lithium source, a carbon source, a phosphorus source and a doped mixed rare earth compound into a dispersant agent for mixing and dispersing; preparing a precursor of a lithium iron phosphate material after wet-grinding, drying and crushing; performing secondary calcining on the precursor in an inert atmosphere; cooling to the room temperature; and crushing by ball-milling to obtain the LiFePO4 cathode material. The material and the preparation method have the advantages that: the prepared LiFePO4 cathode material does not need to separate rare earth elements; and the prepared material has the performance of high capacity, high electric conductivity, stable cycle life, and capacity of performing high-rate discharge.
Description
Technical field
The invention belongs to the electrochemical power source technical field of material, particularly relate to lithium iron phosphate positive material of a kind of mixed rare earth compound doping vario-property and preparation method thereof.Adopt mixed rare earth compound that lithium iron phosphate positive material is mixed, effectively improve the chemical property of material.
Background technology
Lithium ion battery because have the operating voltage height, energy density is big, self-discharge rate is little, stablize advantage such as environmental protection, has become the ideal source of modern digital electronic product.Along with the continuous expansion of its application, the growth of the demand of lithium ion battery is increasing, owing to be subjected to the urgent needs of power source and large-scale energy-storage battery, lithium ion battery should improve and development to direction more efficient, inexpensive, environmental protection simultaneously.
For lithium ion battery, positive electrode is the key factor of decision its chemical property, security performance and Costco Wholesale.The positive electrode that mainly uses is LiCoO now
2, LiNiO
2, and LiMn
2O
2, commercial LiCoO
2The shortcoming that have shortage of resources, cost an arm and a leg, toxicity is big, and can not carry out high rate charge-discharge; LiNiO
2The preparation difficulty, and have safety issue; And LiMn
2O
4Cycle performance and high-temperature behavior still need further to improve.LiFePO
4Be recent years by a kind of anode material for lithium-ion batteries of wide coverage, the Fe resource reserve is abundanter than Co, Ni, Mn, V etc., and is cheap, and Stability Analysis of Structures, aboundresources, security performance are good, nontoxic, environmentally friendly, theoretical capacity is 170mAh.g
-1, the charge and discharge current potential is 3.4V (vs.Li
+/ Li), be lower than the decomposition voltage of most of electrolyte, its cycle performance and good thermal stability, particularly cycle performance is better when high temperature, and good cycle life is arranged.Therefore lithium iron phosphate positive material is one of the most promising anode material for lithium-ion batteries, being the ideal material of lithium ion battery of new generation, also is the field that country " 863 " plan, " 973 " plan and Eleventh Five-Year Plan plans for the development of high-tech industries emphasis are supported.In recent years, improve going deep into of its high rate performance research along with various, the chemical property of such material has reached realistic scale, is acknowledged as the preferred material of high-capacity dynamical and energy-storage battery.
But domestic power lithium-ion battery also is difficult to satisfy the demand of commercialization electric automobile at present, and one of them very big reason is the requirement that anode material for lithium-ion batteries does not satisfy the power battery technology index, influences the overall performance of battery.The subject matter of lithium iron phosphate positive material since in the pure LiFePO4 crystal the tightly packed mode of atom to have caused self electronic conductivity (be 10 under the room temperature
-9～10
-10S/cm) and lithium ion diffusion coefficient (10
-14～10-
16m
2/ s) lower, making it only to discharge and recharge in low range just has high electrochemical performance under the condition, and capacity attenuation is rapid during high current charge-discharge, and high rate capability is poor.Therefore, the big electric current charge and discharge of diffusion coefficient, ionic conductivity and the improvement performance that how to improve lithium ion is that LiFePO4 is used as anode active material of lithium ion battery practicability problem demanding prompt solution.
At the defective that lithium iron phosphate positive material exists, present research mainly concentrates on the following aspects:
(1) adopt suitable synthetic method to control the pattern and the size of product particle, the particle diameter that reduces LiFePO4 is to improve the diffusion coefficient of lithium ion; (2) improve the conductive capability of material in the agent of LiFePO4 particle surface coated with conductive;
(3) in LiFePO4 conductive doped dose (carbon, metal, metal oxide etc.) to improve electronic conductivity;
(4) the doping high volence metal ion forms solid solution, thereby reaches the purpose of activation lattice, raising lithium ion diffusion coefficient.Wherein, LiFePO4 is carried out that valuable metal mixes and carbon coats and becomes a kind of simple but effective method together, can effectively improve conductivity of electrolyte materials and ion expanding rate, improve the high rate performance of material.Select the different metal ion to mix, very big to the property effect of material.
Rare earth element (lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc) and yttrium (Y)) have appraise at the current rate less, electron configuration is stable, reserves abundant, toxicity is little advantage, select rare earth element that LiFePO 4 material is carried out metal position doping vario-property, can effectively improve the chemical property of material.
But rare earth element because its atomic structure, chemistry is close with crystal chemistry character and frequent symbiosis in same mineral, decompose in the resulting mixed rare earth compound in back by rare earths material, separation and Extraction goes out single pure rare earth element, is more complicated and difficulty on chemical technology.Its main cause has two: the one, and physical property and chemical property between the lanthanide series are quite similar, and most rare earth ion radiuses occupy between adjacent two elements, and are very close, all are three stable valence states in the aqueous solution; The 2nd, the affinity of rare earth ion and water is big; because of being subjected to the protection of hydrate, its chemical property is closely similar, separates the very difficulty of purifying; separation between the rare earth element is one of problem the most difficult in rare earth chemistry or even the inorganic chemistry always, also lacks very perfect method so far.Therefore, in the technological process of separation of rare earth elements, consider the separation between the extremely close rare earth element of tens chemical property, the technology more complicated, cost is higher, and causes environmental pollution easily in separation process.
Summary of the invention
The object of the present invention is to provide lithium iron phosphate positive material of a kind of mixed rare earth compound doping vario-property and preparation method thereof, solved rare earth element separating technology more complicated, cost is higher, and causes problems such as environmental pollution in separation process easily.The present invention utilizes physical property and the chemical property between the rare earth element very similar, adopting mixed rare earth compound that LiFePO4 is carried out the Fe position mixes, need not mishmetal is separated, can effectively improve the diffusion velocity and the conductivity of electrolyte materials of lithium ion, improve the cycle performance and the high rate performance of material.
Lithium iron phosphate positive material of the present invention, molecular formula LiFe
1-xRe
xPO
4, wherein Re is a doped source, the scope of x is 0.005～0.15; At least a rare earth element carries out the doping of Fe position to lithium iron phosphate positive material in the mixed rare earth compound; Described rare earth element is: at least a among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, the Y.Be by mixed rare-earth elements the material that doping vario-property obtains to be carried out in its Fe position, this material structure is stable, embedding lithium and to take off the lithium performance good, and cycle performance and chemical property are good.
The preparation method's of the lithium iron phosphate positive material of mixed rare earth compound doping vario-property of the present invention concrete steps are as follows:
(1) total content of mensuration mixed rare earth compound middle rare earth element;
(2) with lithium source, source of iron, rare earth element, phosphorus source according to Li: Fe: Re: P=(0.9～1.1): (1-x): x: 1 mol ratio is prepared burden, after adding the sucrose mixing dispersion of dispersant and 5～10wt%, carry out wet grinding, milling time is 0.5～10 hour, forms slurry; The scope of x is 0.005～0.15;
(3) slurry after will grinding carries out drying under 20～200 ℃ of conditions, simultaneously dispersant is recycled;
(4) dried material is ground after, prepare the precursor of lithium iron phosphate positive material;
(5) precursor with lithium iron phosphate positive material places under inert atmosphere or the reducing atmosphere, 300～500 ℃ of following pre-burnings after 2～12 hours, be cooled to room temperature, after grinding compacting, under inert atmosphere, carry out secondary clacining, calcining heat is 600～1200 ℃, and calcination time is 2～36 hours, is cooled to room temperature again;
(6) LiFe that obtains mixing after pulverizing of the material after will calcining
1-xRe
xPO
4Positive electrode.
Wherein, rare earth element carries out the Fe position and mixes in (5) step, by high temperature solid state reaction, generates LiFe
1-xRe
xPO
4Positive electrode.
Described mixed rare earth compound be by Rare Earth Mine preparation rare earth oxide, chloride, fluoride, carbonate, nitrate, phosphate one or more, contain at least a in rare-earth elements of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc) and the yttrium (Y), do not comprise radioelement promethium (Pm).
Described lithium source is one or more in lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate, lithium acetate, the lithium nitrate; Source of iron is one or more in ferrous oxalate, ferric phosphate, iron oxide, lithium acetate iron, ferric nitrate, the reduced iron powder; The phosphorus source is one or more in ammonium phosphate, ammonium dihydrogen phosphate, the diammonium hydrogen phosphate.
Rare earth element mixes to the Fe position in the LiFePO4 in (5) step, by high temperature solid state reaction, generates LiFe
1-xRe
xPO
4Positive electrode, the mol ratio of Fe element and mixed rare earth compound middle rare earth element is (1-x): x, the scope of x is 0.005～0.15.
Any carries out drying to the slurry after grinding in use solvent recovery drying box, drying machine with centrifugal spray, the constant temperature vacuum drying chamber, simultaneously dispersant is recycled.
Advantage of the present invention is:
(1) directly adopt mixed rare earth compound that LiFePO4 is carried out Fe position doping vario-property, need not rare earth compound is separated, cost is low;
When (2) rare earth element mixes to LiFePO 4 material Fe position, cause the variation of lattice parameter and structure cell, improve conductivity of electrolyte materials and big multiplying power discharging property, but can not cause the loss of material capacity;
(3) the present invention adopts solid-phase synthesis to prepare material, and technology is simple, and cost is low, is applicable to suitability for industrialized production;
(4) prepared material good cycle, Stability Analysis of Structures, good with all kinds of negative materials and electrolyte compatibility, cycle performance is good.
Description of drawings
Fig. 1 is the process chart of example 1.
Fig. 2 is the specific discharge capacity of lithium iron phosphate positive material under different discharge-rates in the example 1.
Embodiment
Below be the specific embodiment of the present invention, technical characterictic of the present invention is described further, but the present invention is not limited to these embodiment.
Lithium carbonate with 0.5mol, 0.95mol ferrous oxalate, containing the mixed rare-earth oxide of 0.05mol rare earth element and the ammonium dihydrogen phosphate of 1mol mixes, add 16.59g sucrose, after adding 200ml absolute ethyl alcohol mixing dispersion, adopt horizontal milling apparatus to grind 1h, use the solvent recovery drying box dry under 120 ℃ of conditions, simultaneously dispersant is recycled; After dried material pulverizing, use planetary ball mill dry ball milling 2h, obtain the lithium iron phosphate positive material precursor.Precursor is placed tube type resistance furnace, at Ar/H
2Under the atmosphere; behind 300 ℃ of following pre-burning 4h; be cooled to room temperature; after grinding compacting, carry out secondary clacining under the protection of inert atmosphere in above-mentioned body of heater, calcining heat is 600 ℃; calcination time 2h; be cooled to room temperature, the material after the employing planetary ball mill will be calcined is crushed to the granularity of requirement, can obtain LiFe
0.95Re
0.05PO
4/ C positive electrode.
LiFe with preparation
0.95Re
0.05PO
4Pole piece that/C positive electrode is made and metal lithium sheet are formed 2025 type button half-cells, carry out charge-discharge test, the result shows that first discharge specific capacity is 135mAh/g under the 0.2C multiplying power, after 3 all charge and discharge cycles, be increased to 141mg/g, capacity does not have significantly sacrificing after 50 weeks of circulation; First discharge specific capacity is 121mAh/g under the 1C multiplying power, and capacity does not have significantly sacrificing after 50 weeks of circulation; First discharge specific capacity is 117mAh/g under the 5C multiplying power, and specific discharge capacity is 114mAh/g after 50 weeks of circulation.Show that this material initial capacity is higher, cycle performance and big multiplying power discharging property are better.
Embodiment 2
Lithium hydroxide with 1mol, 0.49mol di-iron trioxide, containing the mixed rare-earth oxide of 0.02mol rare earth element and the ammonium dihydrogen phosphate of 1mol mixes, add 30.1g sucrose, after adding 300ml absolute ethyl alcohol mixing dispersion, adopt horizontal milling apparatus to grind 4h, use drying machine with centrifugal spray after 180 ℃ of following dryings, use planetary ball mill dry ball milling 2h, obtain the lithium iron phosphate positive material precursor.Precursor is placed pusher furnace, at N
2/ H
2Under the reducing atmosphere; behind 400 ℃ of following pre-burning 2h; be cooled to room temperature; after grinding compacting, carry out secondary clacining under the protection of inert atmosphere in above-mentioned body of heater, calcining heat is 700 ℃; calcination time 5h; be cooled to room temperature, the material after the employing planetary ball mill will be calcined is crushed to the granularity of requirement, can obtain LiFe
0.98Re
0.02PO
4/ C positive electrode.
LiFe with preparation
0.98Re
0.02PO
4Pole piece that/C positive electrode is made and metal lithium sheet are formed 2025 type button half-cells, carry out charge-discharge test, the result shows that first discharge specific capacity is 137mAh/g under the 0.2C multiplying power, after 4 all charge and discharge cycles, be increased to 143mg/g, capacity does not have significantly sacrificing after 50 weeks of circulation; First discharge specific capacity is 123mAh/g under the 1C multiplying power, and capacity does not have significantly sacrificing after 50 weeks of circulation; First discharge specific capacity is 114mAh/g under the 5C multiplying power, and specific discharge capacity is 112mAh/g after 50 weeks of circulation.Show that this material initial capacity is higher, cycle performance and big multiplying power discharging property are better.
Embodiment 3
With the 1mol lithium dihydrogen phosphate, 0.85mol ferrous acetate, the mixed rare-earth oxide that contains the 0.15mol rare earth element mixes, add 18.34g sucrose, after adding 250ml acetone dispersant is disperseed, adopt planetary ball mill to carry out wet grinding, milling time is 8h, use the constant temperature vacuum drying chamber after 200 ℃ of following dryings, use planetary ball mill dry ball milling 2h, obtain the lithium iron phosphate positive material precursor.Precursor is placed pusher furnace, at Ar/H
2Under the atmosphere; behind 500 ℃ of following pre-burning 6h; be cooled to room temperature; after grinding compacting, carry out secondary clacining under the protection of inert atmosphere in above-mentioned body of heater, calcining heat is 800 ℃; calcination time 12h; be cooled to room temperature, the material after the employing planetary ball mill will be calcined is crushed to the granularity of requirement, can obtain LiFe
0.85Re
0.15PO
4/ C positive electrode.
LiFe with preparation
0.85Re
0.15PO
4Pole piece that/C positive electrode is made and metal lithium sheet are formed 2025 type button half-cells, carry out charge-discharge test, the result shows that first discharge specific capacity is 145mAh/g under the 0.2C multiplying power, after 2 all charge and discharge cycles, be increased to 148mg/g, capacity does not have significantly sacrificing after 50 weeks of circulation; First discharge specific capacity is 136mAh/g under the 1C multiplying power, and capacity does not have significantly sacrificing after 50 weeks of circulation; First discharge specific capacity is 132mAh/g under the 5C multiplying power, and specific discharge capacity is 121mAh/g after 50 weeks of circulation.Show that this material initial capacity is higher, cycle performance and big multiplying power discharging property are better.
Embodiment 4
With the 1.1mol lithium acetate, 0.9mol reduced iron powder, the mishmetal carbonate that the 1mol diammonium hydrogen phosphate contains the 0.1mol rare earth element mixes, add 27.74g sucrose, after adding 300ml acetone dispersant is disperseed, adopt planetary ball mill to carry out wet grinding, milling time is 12h, use the constant temperature vacuum drying chamber after 200 ℃ of following dryings, use planetary ball mill dry ball milling 2h, obtain the lithium iron phosphate positive material precursor.Precursor is placed pusher furnace, at Ar/H
2Under the atmosphere; behind 500 ℃ of following pre-burning 10h; be cooled to room temperature; after grinding compacting, carry out secondary clacining under the protection of inert atmosphere in above-mentioned body of heater, calcining heat is 900 ℃; calcination time 16h; be cooled to room temperature, the material after the employing planetary ball mill will be calcined is crushed to the granularity of requirement, can obtain Li
1.1Fe
0.9Re
0.1PO
4/ C positive electrode.
Li with preparation
1.1Fe
0.9Re
0.1PO
4Pole piece that/C positive electrode is made and metal lithium sheet are formed 2025 type button half-cells, carry out charge-discharge test, the result shows that first discharge specific capacity is 128mAh/g under the 0.2C multiplying power, after 5 all charge and discharge cycles, be increased to 135mg/g, capacity does not have significantly sacrificing after 50 weeks of circulation; First discharge specific capacity is 123mAh/g under the 1C multiplying power, and capacity does not have significantly sacrificing after 50 weeks of circulation; First discharge specific capacity is 116mAh/g under the 5C multiplying power, and specific discharge capacity is 112mAh/g after 50 weeks of circulation.Show that this material initial capacity is higher, cycle performance and big multiplying power discharging property are better.
Embodiment 5
With the 1.0mol lithium nitrate, 0.93mol ferric phosphate, the mishmetal phosphate that contains the 0.07mol rare earth ion mixes, add 20.92g sucrose, after adding 300ml deionized water dispersant is disperseed, adopt planetary ball mill to carry out wet grinding, milling time is 0.5h, use the constant temperature vacuum drying chamber after 80 ℃ of following dryings, use planetary ball mill dry ball milling 1h, obtain the lithium iron phosphate positive material precursor.Precursor is placed chamber type electric resistance furnace; under He atmosphere; behind 500 ℃ of following pre-burning 8h, be cooled to room temperature, after the grinding compacting; in above-mentioned body of heater, carry out secondary clacining under the protection of inert atmosphere; calcining heat is 1200 ℃, and calcination time 20h is cooled to room temperature; material after the employing planetary ball mill will be calcined is crushed to the granularity of requirement, can obtain LiFe
0.93Re
0.07PO
4/ C positive electrode.
LiFe with preparation
0.93Re
0.07PO
4Pole piece that/C positive electrode is made and metal lithium sheet are formed 2025 type button half-cells, carry out charge-discharge test, the result shows that first discharge specific capacity is 143mAh/g under the 0.2C multiplying power, after 3 all charge and discharge cycles, be increased to 146mg/g, capacity does not have significantly sacrificing after 50 weeks of circulation; First discharge specific capacity is 137mAh/g under the 1C multiplying power, and capacity does not have significantly sacrificing after 50 weeks of circulation; First discharge specific capacity is 128mAh/g under the 5C multiplying power, and specific discharge capacity is 119mAh/g after 50 weeks of circulation.Show that this material initial capacity is higher, cycle performance and big multiplying power discharging property are better.
Embodiment 6
With the 1.05mol lithium carbonate, 0.9mol ferric phosphate, the mishmetal phosphate that contains the 0.1mol rare earth ion mixes, add 20.92g sucrose, after adding 280ml alcohol dispersant mixes dispersion, adopt planetary ball mill to carry out wet grinding, milling time is 2h, use the constant temperature vacuum drying chamber after 160 ℃ of following dryings, use planetary ball mill dry ball milling 2h, obtain the lithium iron phosphate positive material precursor.Precursor is placed chamber type electric resistance furnace; under He atmosphere; behind 400 ℃ of following pre-burning 8h, be cooled to room temperature, after the grinding compacting; in above-mentioned body of heater, carry out secondary clacining under the protection of inert atmosphere; calcining heat is 1000 ℃, and calcination time 24h is cooled to room temperature; material after the employing planetary ball mill will be calcined is crushed to the granularity of requirement, can obtain Li
1.05Fe
0.9Re
0.1PO
4/ C positive electrode.Li with preparation
1.05Fe
0.9Re
0.1PO
4Pole piece that/C positive electrode is made and metal lithium sheet are formed 2025 type button half-cells, carry out charge-discharge test, the result shows that first discharge specific capacity is 140mAh/g under the 0.2C multiplying power, discharge and recharge activation through 4 weeks after, be increased to 142mg/g, capacity does not have significantly sacrificing after 50 weeks of circulation; First discharge specific capacity is 133mAh/g under the 1C multiplying power, and capacity does not have significantly sacrificing after 50 weeks of circulation; First discharge specific capacity is 126mAh/g under the 5C multiplying power, and specific discharge capacity is 121mAh/g after 50 weeks of circulation.Show that this material initial capacity is higher, cycle performance and big multiplying power discharging property are better.
Claims (7)
1. the lithium iron phosphate positive material of a mixed rare earth compound doping vario-property is characterized in that, the lithium iron phosphate positive material of described doping vario-property molecular formula LiFe
1-xRe
xPO
4Expression, wherein Re is a doped source, the scope of x is 0.005～0.15; At least a rare earth element carries out the doping of Fe position to lithium iron phosphate positive material in the mixed rare earth compound; Described rare earth element is: at least a among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, the Y.
2. the preparation method of the described mixed rare earth compound doping vario-property of claim 1 lithium iron phosphate positive material is characterized in that processing step is:
(1) total content of mensuration mixed rare earth compound middle rare earth element;
(2) with lithium source, source of iron, rare earth element, phosphorus source according to Li: Fe: Re: P=(0.9～1.1): (1-x): x: 1 mol ratio is prepared burden, after adding the sucrose mixing dispersion of dispersant and 5～10wt%, carry out wet grinding, milling time is 0.5～10 hour, forms slurry; The scope of x is 0.005～0.15;
(3) slurry after will grinding carries out drying under 20～200 ℃ of conditions, simultaneously dispersant is recycled;
(4) dried material is ground after, prepare the precursor of lithium iron phosphate positive material;
(5) precursor with lithium iron phosphate positive material places under inert atmosphere or the reducing atmosphere, 300～500 ℃ of following pre-burnings after 2～12 hours, be cooled to room temperature, after grinding compacting, under inert atmosphere, carry out secondary clacining, calcining heat is 600～1200 ℃, and calcination time is 2～36 hours, is cooled to room temperature again;
(6) LiFe that obtains mixing after pulverizing of the material after will calcining
1-xRe
xPO
4Positive electrode.
3. according to the preparation method of the described mixed rare earth compound doping vario-property of claim 2 lithium iron phosphate positive material, it is characterized in that, described mixed rare earth compound be by Rare Earth Mine preparation rare earth oxide, chloride, fluoride, carbonate, nitrate, phosphate one or more, contain at least a among rare-earth elements La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, the Y.
4. according to the preparation method of the described mixed rare earth compound doping vario-property of claim 2 lithium iron phosphate positive material, it is characterized in that described lithium source is one or more in lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate, lithium acetate, the lithium nitrate; Source of iron is one or more in ferrous oxalate, ferric phosphate, iron oxide, lithium acetate iron, ferric nitrate, the reduced iron powder; The phosphorus source is one or more in ammonium phosphate, ammonium dihydrogen phosphate, the diammonium hydrogen phosphate.
5. according to the preparation method of the described mixed rare earth compound doping vario-property of claim 2 lithium iron phosphate positive material, it is characterized in that rare earth element mixes to the Fe position in the LiFePO4 in (5) step,, generate LiFe by high temperature solid state reaction
1-xRe
xPO
4Positive electrode; The mol ratio of Fe element and mixed rare earth compound middle rare earth element is (1-x): x, and the scope of x is 0.005～0.15.
6. according to the preparation method of the described mixed rare earth compound doping vario-property of claim 2 lithium iron phosphate positive material, it is characterized in that, any carries out drying to the slurry after grinding in use solvent recovery drying box, drying machine with centrifugal spray, the constant temperature vacuum drying chamber, simultaneously dispersant is recycled.
7. according to the preparation method of the described mixed rare earth compound doping vario-property of claim 2 lithium iron phosphate positive material, it is characterized in that described inert atmosphere or reducing atmosphere are He, Ar, N
2, H
2The mixing of one or more gases.
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| CN107834059A (en) * | 2017-07-08 | 2018-03-23 | 郑春燕 | A kind of preparation technology of novel composite electrode material |
| CN107834066A (en) * | 2017-07-09 | 2018-03-23 | 郑春燕 | A kind of high conductivity combination electrode material and technique for adulterating manganese |
| CN107611432A (en) * | 2017-09-10 | 2018-01-19 | 绵阳梨坪科技有限公司 | The preparation method of the good rare-earth lithium iron phosphorus compound of electric conductivity |
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| CN108906026A (en) * | 2018-08-07 | 2018-11-30 | 吉林大学 | Lanthanum cerium codoping titanium oxide material and preparation method based on mischmetal carbonate |
| CN108906026B (en) * | 2018-08-07 | 2021-04-16 | 吉林大学 | Lanthanum-cerium co-doped titanium oxide material based on mixed rare earth carbonate and preparation method thereof |
| CN113410464A (en) * | 2021-06-15 | 2021-09-17 | 南开大学 | Multi-element rare earth doped high nickel oxide lithium battery positive electrode material and preparation method thereof |
| CN113410464B (en) * | 2021-06-15 | 2023-03-14 | 南开大学 | Multi-element rare earth doped high-nickel oxide lithium battery positive electrode material and preparation method thereof |
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