CN101841021B - Composite anode material of lithium iron phosphate and lithium vanadium phosphate and preparation method thereof - Google Patents
Composite anode material of lithium iron phosphate and lithium vanadium phosphate and preparation method thereof Download PDFInfo
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- CN101841021B CN101841021B CN2010101825643A CN201010182564A CN101841021B CN 101841021 B CN101841021 B CN 101841021B CN 2010101825643 A CN2010101825643 A CN 2010101825643A CN 201010182564 A CN201010182564 A CN 201010182564A CN 101841021 B CN101841021 B CN 101841021B
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Abstract
The invention relates to a composite anode material of lithium iron phosphate and lithium vanadium phosphate and a preparation method thereof. The composite anode material is prepared from a nanometer vanadium compound, a nanometer phosphorous compound, a nanometer lithium compound and a nanometer iron compound in a mol ratio of 1:1-1.5:1-2:1-1.5. The composite anode material of lithium iron phosphate and lithium vanadium phosphate prepared by the method has the advantages of good chemical performance and processing performance, simple preparation method and process and reaction device, and easily-controlled condition.
Description
Technical field
The present invention relates to a kind of LiFePO4 and phosphoric acid vanadium lithium composite positive pole and manufacturing approach thereof, particularly relate to a kind of LiFePO4 and phosphoric acid vanadium lithium composite material and manufacturing approach thereof, belong to the lithium ion battery field as anode material for lithium-ion batteries.
Background technology
Along with the exhaustion gradually of main natural resources such as coal, oil, energy crisis has become one of human following key subjects that must solve.The novel high-energy chemical power source of green non-pollution has become competitively hot of research and development of countries in the world at present.
Lithium ion battery is a kind of novel chemical power source, embeds with two abilities respectively and the compound of deviating from lithium ion constitutes as both positive and negative polarity reversiblely.When battery charge, lithium ion takes off embedding and comes out from positive pole, in negative pole, embed; Lithium ion takes off embedding and comes out during discharge from negative pole, in positive pole, embeds.Lithium ion battery is widely used in notebook computer, mobile phone and other portable electronics owing to have advantages such as high-energy-density, high voltage, pollution-free, cycle life height, memory-less effect.
Lithium ion battery is main with low capacity, low battery power still at present; In big capacity, in the not large-scale production as yet of high-power lithium ion battery, make lithium ion battery in middle large-capacity ups, medium-and-large-sized energy-storage battery, electric tool, electric automobile, not be used widely as yet.One of them major reason is that anode material for lithium-ion batteries is not obtained important breakthrough as yet.
Positive electrode is the important component part of lithium ion battery.Studying maximum positive electrodes so far is LiCoO
2, LiNiO
2, LiMn
2O
4And the derivative of above three kinds of materials, like LiNi
0.8Co
0.2O
2, LiNi
1/3Co
1/3Mn
1/3O
2Deng.
LiCoO
2Be the positive electrode of unique large-scale commercial, present commercialization lithium ion battery more than 90% adopts LiCoO
2As positive electrode.LiCoO
2The research comparative maturity, high comprehensive performance, but cost an arm and a leg, capacity is lower, has certain safety issue.
LiNiO
2Cost is lower, and capacity is higher, but the preparation difficulty, there are comparatively serious safety problem in the consistency of material property and poor reproducibility.LiNi
0.8Co
0.2O
2Can regard LiNiO as
2And LiCoO
2Solid solution, have LiNiO concurrently
2And LiCoO
2Advantage, once it is believed that it is most possibly to replace LiCoO
2Novel anode material, but still have shortcomings such as synthesis condition comparatively harsh (needing oxygen atmosphere), fail safe be relatively poor, combination property haves much room for improvement; Owing to contain the Co of more costliness, cost is also higher simultaneously.
Spinelle LiMn
2O
4Cost is low, and fail safe is good, but cycle performance especially high temperature cyclic performance is poor, certain dissolubility is arranged in electrolyte, storge quality is poor.
Novel ternary compound oxides nickle cobalt lithium manganate (LiNi
1/3Co
1/3Mn
1/3O
2) material concentrated LiCoO
2, LiNiO
2, LiMn
2O
4Advantage separately Deng material: cost and LiNi
0.8Co
0.2O
2Quite, reversible capacity is big, Stability Analysis of Structures, and fail safe is better, between LiNi
0.8Co
0.2O
2And LiMn
2O
4Between, good cycle, easily synthetic; But owing to contain the Co of more costliness, cost is also higher.The big capacity of centering, in high-power lithium ion battery, the cost of positive electrode, high-temperature behavior, fail safe are very important.
Above-mentioned LiCoO
2, LiNiO
2, LiMn
2O
4And the derivative positive electrode still can not meet the demands.Therefore, research and development can be used for big capacity, in the novel anode material of high-power lithium ion battery become current focus.
(A is an alkali metal, and M is both combinations of CoFe: LiFeCOPO to disclose AyMPO4 first from the NTT of Japan in 1996
4) the anode material of lithium battery of olivine structural after, research crowds such as the upright John.B.Goodenough of university of Texas, USA in 1997 have also then reported LiFePO
4Invertibity the characteristic of the lithium of moving into, the U.S. and Japan coincidentally deliver olivine structural (LiMPO
4), make this material receive great attention, and cause extensive studies and development rapidly.
The LiFePO of quadrature olivine structural
4Positive electrode becomes new research focus both at home and abroad gradually.Primary Study shows that this novel anode material has been concentrated LiCoO
2, LiNiO
2, LiMn
2O
4And the advantage separately of derivative positive electrode: do not contain noble element, low in raw material cost, resource are greatly abundant; Operating voltage moderate (3.4V); Platform identity is good, and voltage pole is (can match in excellence or beauty with stabilized voltage power supply) steadily; Theoretical capacity big (170mAh/g); Stability Analysis of Structures, security performance splendid (O and P make material be difficult to analyse oxygen and decompose with the strong covalent bond strong bonded); High-temperature behavior and thermal stability obviously are superior to other known positive electrode; Good cycle; Volume-diminished during charging, the bulk effect when cooperating with carbon negative pole material is good; Good with most of electrolyte system compatibility, storge quality is good; Nontoxic, be real green material.
LiFePO4 is the thing that just occurred in recent years as anode material of lithium battery, and its security performance and cycle life are better, and these are the most important technical indicator of electrokinetic cell just also.Lithium iron phosphate positive material is made high capacity lithium ion battery and more is prone to the series connection use, to satisfy the needs that electric motor car frequently discharges and recharges.Having advantages such as nontoxic, pollution-free, that security performance is good, raw material wide material sources, low price, and the life-span is long, is the desirable positive electrode of lithium ion battery of new generation.
Yet the shortcoming that the LiFePO4 bulk density is low receives people's ignorance and avoidance always, is not resolved as yet, has hindered the practical application of material.The solid density of cobalt acid lithium is 5.1g/cm3, and the tap density of commodity cobalt acid lithium is generally 2.0-2.4g/cm3; And the solid density of LiFePO4 is merely 3.6g/cm3, and itself is just much lower than cobalt acid lithium.
For improving conductivity, people mix conductive carbon material, have significantly reduced the bulk density of material again, make the tap density of general carbon dope LiFePO4 have only 1.0-1.2g/cm3.So low bulk density makes that the volume and capacity ratio of LiFePO4 is more much lower than the sour lithium of cobalt, and the battery volume of processing will be very huge, not only have no advantage can say, and be difficult to be applied to reality.
Therefore, the bulk density of raising LiFePO4 and volume and capacity ratio have the decision meaning to the practicability of LiFePO4.
Phosphoric acid vanadium lithium is the compound of monocline, and being considered to possibly be than the better polyanion type of LiFePO4 performance positive electrode.Vanadium in the phosphoric acid vanadium lithium can be for+2 ,+3 ,+4 ,+5 four kinds of valence states, there are 5 lithium ions can in material, take off embedding in theory, theoretical capacity can reach 332mAh/g.Phosphoric acid vanadium lithium has 1.7-2.0,3.61,3.69,4.1, five charge and discharge platform of 4.6-4.8, and it is right that the lithium ion of different platform takes off the vanadium particle electricity that embedding corresponds respectively to different valence state.
Phosphoric acid vanadium lithium is owing to have theoretical specific capacity high and low temperature performance and Heat stability is good.Advantages such as cycle performance is excellent, cost is low enjoy people's attention.
Summary of the invention
A kind of LiFePO4 and phosphoric acid vanadium lithium composite positive pole and manufacturing approach thereof have been the purpose of this invention is to provide.
For realizing the foregoing invention purpose; LiFePO4 provided by the present invention and phosphoric acid vanadium lithium composite positive pole are to be raw material by nanometer vanadium source compound, nanometer P source compound, nanometer Li source compound and nanometer Fe source compound; Mixed composite powder, composite powder again with CNT fully mixed LiFePO4 and phosphoric acid vanadium lithium composite positive pole.
In above-mentioned LiFePO4 and phosphoric acid vanadium lithium composite positive pole, described nanometer vanadium source compound, nanometer P source compound, nanometer Li source compound and nanometer Fe source compound are 1 according to vanadium, phosphorus, lithium, ferro element mol ratio: the mixed of 1-1.5: 1-2: 1-1.5.The percentage by weight of described composite powder and CNT is 10-80%: 20-90%.
In above-mentioned LiFePO4 and phosphoric acid vanadium lithium composite positive pole, described nanometer vanadium source compound is one or more in vanadium dioxide, vanadic oxide, metavanadic acid ammonia, carbonic acid vanadium, the vanadium tetrachloride, and granularity is 1-100nm, and purity is 99%～99.99%.Described nanometer P source compound is one or more in phosphoric acid, triammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, sodium hydrogen phosphate, lithium dihydrogen phosphate, phosphoric acid hydrogen two lithiums; Granularity is 1-100nm, and purity is 99%～99.99%.Said nanometer Li source compound is one or more in lithium nitrate, lithium chloride, lithium dihydrogen phosphate, lithium sulfate, lithium acetate, lithium hydroxide, the lithium carbonate, and granularity is 1-100nm, and purity is 99%～99.99%.Described nanometer Fe source compound is one or more in ferrous sulfate, ferrous ammonium phosphate, ferrous oxalate, ferric nitrate, ferric sulfate, the ferrous acetate, and granularity is 1-100nm, and purity is 99%～99.99%.Described CNT granularity is 10-500nm.
For realizing the foregoing invention purpose, the present invention has provided the manufacturing approach of a kind of LiFePO4 and phosphoric acid vanadium lithium composite positive pole, the steps include:
1) be 1 in vanadium, phosphorus, lithium, ferro element mol ratio: the ratio of 1-1.5: 1-2: 1-1.5 takes by weighing nanometer vanadium source compound, nanometer P source compound, nanometer Li source compound and nanometer Fe source compound; Put into nanometer high pressure, high temperature vapor mixer; High-temperature vapour source temperature scope is 100-600 ℃ in the mixer, 60～300 rev/mins of mixing speeds, and programming rate is per hour 50-200 ℃; 50-200 ℃ of control mixer temperature; Controlled pressure 0-50MPa, mixes pulping at 5-20 hour heat-insulation pressure keeping time in vacuum state;
2) mixed pulp flows into through pipeline has in the high-temperature vacuum sintering furnace of one or more protections in inert gas helium, neon, the argon, control vacuum degree 10
-5-10
-3Pa, pressurization 1000-6000psi (pound/square inch) is equivalent to the 6.9-41.4Mpa that pressurizes, and per hour 100 ℃ of control programming rates are warming up to 400-1000 ℃, keep 5-20 hour, make nanocomposite reunion piece;
3) place grinding in ball grinder to use powder the nanocomposite piece of reuniting into 1um-50um;
4) CNT of percetage by weight 20-90% is put into nanometer high pressure, high temperature vapor mixer; The employing temperature range is that mixing is introduced with the powder of 10-80% nanocomposite in 100-600 ℃ high-temperature vapour source; 90-200 ℃ of control mixer temperature; Speed of agitator is 1-60 rev/min, mixes 2-10 hour.
In the manufacturing approach of above-mentioned LiFePO4 and phosphoric acid vanadium lithium composite positive pole, described high-temperature vapour source is at least a of water, hydro carbons, ethyl acetate, acetone, toluene, ethanol, glycerine, oxolane, carrene, carbon tetrachloride, phenol, sulfuric acid, hydrochloric acid, nitric acid, acetate and oxalic acid.
Advantage of the present invention does, manufacturing approach craft and consersion unit are simple, and condition is controlled easily; The positive electrode chemical property that makes is good, and processing characteristics is good.
Embodiment
Embodiment one:
Is 1: 1: 1 with nano vanadium dioxide, nanometer potassium phosphate, nanometer lithium hydroxide and nanometer ferrous sulfate by vanadium, phosphorus, lithium, ferro element mol ratio: 1 mixed; Put into nanometer high pressure, high temperature vapor mixer, adopt mol ratio be 1: 1 anhydrous C4～C12 hydrocarbon liquids and 5-10% acid solution as vapor source, the steam temperature scope is 100-200 ℃ in the mixer; 60～300 rev/mins of mixing speeds; Programming rate is per hour 50 ℃, 50 ℃ of control mixer temperature, controlled pressure 5MPa; 5 hours heat-insulation pressure keeping time, in vacuum state, mix pulping; Mixed pulp flows into through pipeline to be had in the high-temperature vacuum sintering furnace of inert gas helium-atmosphere, control vacuum degree 10
-5-10
-3Pa, pressurization 1000-6000psi, per hour 100 ℃ of control programming rates are warming up to 800 ℃, keep 10 hours, make nanocomposite reunion piece; Place grinding in ball grinder to use powder the nanocomposite piece of reuniting into 1um-50um; The CNT of percentage by weight 80% is put into nanometer high pressure, high temperature vapor mixer; Adopting steam is that carrier is introduced mixing with the powder of 20% nanocomposite; 150 ℃ of control mixer temperature, speed of agitator is 1-60 rev/min, mixes 10 hours.
Through the LiFePO 4 material that said method makes, the 0.2C discharge capacity is 136mAh/g, and 50 times circulation back capacity remains 96.2%.
Embodiment two:
Is 1: 1: 2 with nanometer vanadium tetrachloride, nanometer sodium phosphate, nano-calcium carbonate lithium and nanometer ferrous oxalate by vanadium, phosphorus, lithium, ferro element mol ratio: 1 mixed; Put into nanometer high pressure, high temperature vapor mixer, adopt mol ratio be 1: 0.5 anhydrous C4～C12 hydrocarbon liquids and 5-10% acid solution as vapor source, the steam temperature scope is 100-300 ℃ in the mixer; 60～300 rev/mins of mixing speeds; Programming rate is per hour 50 ℃, 50 ℃ of control mixer temperature, controlled pressure 10MPa; 5 hours heat-insulation pressure keeping time, in vacuum state, mix pulping; Mixed pulp is controlled vacuum degree 10 in pipeline flows into the high-temperature vacuum sintering furnace of one or more protections that inert gas helium, neon, argon are arranged
-5-10
-3Pa, pressurization 1000-6000psi, per hour 100 ℃ of control programming rates are warming up to 1000 ℃, keep 20 hours, make nanocomposite reunion piece; Place grinding in ball grinder to use powder the nanocomposite piece of reuniting into 1um-50um; The CNT of percentage by weight 20% is put into nanometer high pressure, high temperature vapor mixer; Adopting steam is that carrier is introduced mixing with the powder of 80% nanocomposite; 200 ℃ of control mixer temperature, speed of agitator is 1-60 rev/min, mixes 10 hours.
Through the LiFePO 4 material that said method makes, the 0.2C discharge capacity is 149mAh/g, and 50 times circulation back capacity remains 95.3%.
Embodiment three:
Is 1: 1.5: 1.5 with nano-calcium carbonate vanadium, nanometer sodium dihydrogen phosphate, nanometer lithium chloride and nanometer ferric sulfate by vanadium, phosphorus, lithium, ferro element mol ratio: 1.5 mixed; Put into nanometer high pressure, high temperature vapor mixer, adopt mol ratio be 1: 1 anhydrous C4～C12 hydrocarbon liquids and 5-10% acid solution as vapor source, the steam temperature scope is 200-300 ℃ in the mixer; 60～300 rev/mins of mixing speeds; Programming rate is per hour 50 ℃, 50 ℃ of control mixer temperature, controlled pressure 5MPa; 5 hours heat-insulation pressure keeping time, in vacuum state, mix pulping; Mixed pulp flows into through pipeline to be had in the high-temperature vacuum sintering furnace of inert gas helium-atmosphere, control vacuum degree 10
-5-10
-3Pa, pressurization 1000-6000psi, per hour 100 ℃ of control programming rates are warming up to 900 ℃, keep 10 hours, make nanocomposite reunion piece; Place grinding in ball grinder to use powder the nanocomposite piece of reuniting into 1um-50um; The CNT of percentage by weight 60% is put into nanometer high pressure, high temperature vapor mixer, and adopting steam is that carrier is introduced mixing with the powder of 40% nanocomposite, 150 ℃ of control mixer temperature, and speed of agitator is 1-60 rev/min, mixes 6 hours.
Through the LiFePO 4 material that said method makes, the 0.2C discharge capacity is 128mAh/g, and 50 times circulation back capacity remains 97.8%.
Claims (7)
1. the manufacturing approach of LiFePO4 and phosphoric acid vanadium lithium composite positive pole the steps include:
1) be 1 in vanadium, phosphorus, lithium, ferro element mol ratio: the ratio of 1-1.5: 1-2: 1-1.5 takes by weighing nanometer vanadium source compound, nanometer P source compound, nanometer Li source compound and nanometer Fe source compound; Put into nanometer high pressure, high temperature vapor mixer; High-temperature vapour source temperature scope is 100-600 ℃ in the mixer, 60～300 rev/mins of mixing speeds, and programming rate is per hour 50-200 ℃; 50-200 ℃ of control mixer temperature; Controlled pressure 0-50MPa, mixes pulping at 5-20 hour heat-insulation pressure keeping time in vacuum state;
2) mixed pulp flows into through pipeline has in the high-temperature vacuum sintering furnace of one or more protections in inert gas helium, neon, the argon, control vacuum degree 10
-5-10
-3Pa, pressurization 1000-6000psi, per hour 100 ℃ of control programming rates are warming up to 400-1000 ℃, keep 5-20 hour, make nanocomposite reunion piece;
3) place grinding in ball grinder to become the powder of 1 μ m-50 μ m the nanocomposite piece of reuniting;
4) CNT of percetage by weight 20-90% is put into nanometer high pressure, high temperature vapor mixer; The employing temperature range is that mixing is introduced with the powder of 10-80% nanocomposite in 100-600 ℃ high-temperature vapour source; 90-200 ℃ of control mixer temperature; Speed of agitator is 1-60 rev/min, mixes 2-10 hour.
2. the manufacturing approach of a kind of LiFePO4 according to claim 1 and phosphoric acid vanadium lithium composite positive pole is characterized in that: said high-temperature vapour source is at least a in water, hydro carbons, ethyl acetate, acetone, ethanol, glycerine, oxolane, carrene, carbon tetrachloride, phenol, sulfuric acid, hydrochloric acid, nitric acid, acetate and the oxalic acid.
3. the manufacturing approach of a kind of LiFePO4 according to claim 1 and phosphoric acid vanadium lithium composite positive pole; It is characterized in that: described nanometer vanadium source compound is one or more in vanadium dioxide, vanadic oxide, metavanadic acid ammonia, carbonic acid vanadium, the vanadium tetrachloride; Granularity is 1-100nm, and purity is 99%～99.99%.
4. the manufacturing approach of a kind of LiFePO4 according to claim 1 and phosphoric acid vanadium lithium composite positive pole; It is characterized in that: described nanometer P source compound is one or more in phosphoric acid, triammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, sodium hydrogen phosphate, lithium dihydrogen phosphate, phosphoric acid hydrogen two lithiums; Granularity is 1-100nm, and purity is 99%～99.99%.
5. the manufacturing approach of a kind of LiFePO4 according to claim 1 and phosphoric acid vanadium lithium composite positive pole; It is characterized in that: said nanometer Li source compound is one or more in lithium nitrate, lithium chloride, lithium dihydrogen phosphate, lithium sulfate, lithium acetate, lithium hydroxide, the lithium carbonate; Granularity is 1-100nm, and purity is 99%～99.99%.
6. the manufacturing approach of a kind of LiFePO4 according to claim 1 and phosphoric acid vanadium lithium composite positive pole; It is characterized in that: described nanometer Fe source compound is one or more in ferrous sulfate, ferrous ammonium phosphate, ferrous oxalate, ferric nitrate, ferric sulfate, the ferrous acetate; Granularity is 1-100nm, and purity is 99%～99.99%.
7. the manufacturing approach of a kind of LiFePO4 according to claim 1 and phosphoric acid vanadium lithium composite positive pole is characterized in that: described CNT granularity is 10-500nm.
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|---|---|---|---|
| CN2010101825643A CN101841021B (en) | 2010-05-26 | 2010-05-26 | Composite anode material of lithium iron phosphate and lithium vanadium phosphate and preparation method thereof |
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| CN101841021B true CN101841021B (en) | 2012-09-05 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101997112B (en) * | 2010-11-02 | 2013-04-17 | 中南大学 | Method for preparing lithium iron phosphate-lithium vanadium phosphate composite precursor from coulsonite |
| CN102208620A (en) * | 2011-04-19 | 2011-10-05 | 哈尔滨工业大学 | Method for preparing lithium ion battery anode material xLiFePO4.yLi3V2(PO4)3 |
| CN102208619B (en) * | 2011-04-19 | 2013-09-04 | 哈尔滨工业大学 | Method for preparing magnesium-doped xLiFePO4.yLi3V2(PO4)3 lithium ion battery anode material |
| KR101561373B1 (en) * | 2013-01-10 | 2015-10-19 | 주식회사 엘지화학 | Method for preparing lithium iron phosphate nanopowder |
| CN104485448B (en) * | 2014-12-23 | 2017-05-24 | 深圳市德睿新能源科技有限公司 | Method for one-step synthesis of LiFePO4-Li3V2(PO4)3composite material with solvothermal method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101114709A (en) * | 2007-08-10 | 2008-01-30 | 武汉大学 | Lithium ion battery composite anode material LiFePO4-Li3V2(PO4)3/C and method for making same |
| CN101214942A (en) * | 2008-01-08 | 2008-07-09 | 上海大学 | Electron beam irradiation synthesis method for LixMy(PO4)z compounds |
| CN101262058A (en) * | 2008-04-15 | 2008-09-10 | 中南大学 | An anode material for compound lithium ion battery |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101114709A (en) * | 2007-08-10 | 2008-01-30 | 武汉大学 | Lithium ion battery composite anode material LiFePO4-Li3V2(PO4)3/C and method for making same |
| CN101214942A (en) * | 2008-01-08 | 2008-07-09 | 上海大学 | Electron beam irradiation synthesis method for LixMy(PO4)z compounds |
| CN101262058A (en) * | 2008-04-15 | 2008-09-10 | 中南大学 | An anode material for compound lithium ion battery |
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