CN108448113A - Preparation method of doped modified lithium iron phosphate positive-grade material - Google Patents
Preparation method of doped modified lithium iron phosphate positive-grade material Download PDFInfo
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- CN108448113A CN108448113A CN201810271437.7A CN201810271437A CN108448113A CN 108448113 A CN108448113 A CN 108448113A CN 201810271437 A CN201810271437 A CN 201810271437A CN 108448113 A CN108448113 A CN 108448113A
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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Abstract
The invention provides a preparation method of lithium iron phosphate as a lithium ion battery anode material, which comprises the steps of taking battery-grade lithium carbonate doped with magnesium or magnesium and rare earth as a lithium source, mixing the lithium source with an iron source, a phosphorus source and a carbon source, grinding, drying to obtain a doped and modified lithium iron phosphate precursor, and roasting the precursor to obtain a lithium iron phosphate anode material product; the Mg content of the battery-grade lithium carbonate is 0.06-1.75%. The preparation method has short grinding time and is energy-saving, is beneficial to realizing the uniform doping of magnesium, cerium or lanthanum to the lithium iron phosphate, and is particularly convenient to realize the doping of magnesium, cerium or lanthanum to the lithium position of the lithium iron phosphate. According to the invention, rare earth and/or magnesium are compounded in the battery-grade lithium carbonate for preparing the lithium iron phosphate, so that the grinding time is reduced, the cost is lower, and the lithium iron phosphate anode material prepared by the method has superior discharge capacity, cycle performance and rate capability, and better meets the application requirements.
Description
Technical field
The present invention relates to a kind of preparation methods of lithium ion battery anode material lithium iron phosphate, more particularly to a kind of phosphoric acid
The doping modification method of iron lithium anode material belongs to anode material for lithium-ion batteries technical field.
Background technology
LiFePO4 is obtained as a kind of important lithium ion battery cathode material in electric vehicle, Chu Neng Installed are set etc.
Extensive use.Since the electronic conductivity of LiFePO4, ionic conductivity are low, in order to improve the electrical property of LiFePO4, usually
Take following manner：Reduce material particle size, coated with conductive layer, ion doping.Ion doping method is primarily referred to as in LiFePO4 crystalline substance
Cation position in lattice adulterates the metal ion of some good conductivities, changes the size of crystal grain, causes the lattice defect of material,
To improve the conductivity of electronics and the diffusion rate of lithium ion in crystal grain, and then reaches and improve LiFePO4 Material electrical property
Purpose.Currently, the metal ion of doping mainly has Ti4+、Zn2+、Mn2+、La3+、Ce3+、V3+、Mg2+Deng.
Cation position doping in LiFePO4 lattice divides the doping of lithium position and the doping of iron position.Wherein, the doping of lithium position is common
Doped chemical be Mg2+、La3+、Ce3+Deng.It is existing studies have shown that 2-3 kind impurity multiple-composite doped spinel be better than a kind of impurity
Unitary doping.
In lithium ion battery cathode material（LiFePO4, ternary material etc.）Preparation in, the doping of impurity magnesium, rare earth makes
It is more with obtaining.Currently, the Magnesium-doped of LiFePO4 is typically employed in synthesis presoma source of iron（Ferrous oxalate, ferric phosphate etc.）
When, so that micro magnesium is co-precipitated in source of iron, or use the acylate of magnesium in dispensing（Ethanedioic acid magnesium etc.）, inorganic acid salt
（Such as magnesium nitrate）As dopant.But the more difficult quantitative control of magnesium is mixed with coprecipitation into ferrous oxalate；If when compounding, mixing with
The compound of a small amount of magnesium or a small amount of rare earth it is compound doped, then it is more difficult to be uniformly mixed, and to compounding, mixing, the requirement ground
It is higher.
Related application is such as：1, CN 101070149A disclose a kind of LiFePO 4 material prepared by vacuum carbon reduction
And method, include the following steps：Fe source compound, Li source compound and doping metals compound are pressed P ﹕ Fe ﹕ Li ﹕ M by the first step
Molar ratio be 1 ﹕, 1 ﹕ 1：（0.001~0.05）Ratio mixing, wherein M state doping metals；Second step is by the above-mentioned first step
The mixture being mixed to get is placed in vacuum high-energy ball milling tank, is vacuumized, ball milling；Carbonaceous reducing agent is pressed Fe ﹕ C mole by third step
It than the ratio of 1 ﹕ 0.8~1.6, is added in the good mixture of above-mentioned second step ball-milling treatment, vacuumizes, continue ball milling, obtain
Pre-reaction material；Above-mentioned reaction precursor is transferred in vacuum reaction stove by the 4th step, is passed through nitrogen, is vacuumized, heats, permanent
Nitrogen is passed through under temperature again, sealing is cooled to room temperature, and obtains the metal-doped lithium iron phosphate positive material of carbon coated；The doping
Metallic compound includes one or more of aluminium dihydrogen phosphate, zinc oxide, magnesia, cobalt oxide.2, CN 103137966A are public
A kind of preparation method of doping vario-property lithium iron phosphate positive material is opened, by lithium source, source of iron, phosphorus source, doped source and dispersant
It is placed in agitating ball mill and is uniformly mixed with substances such as binders, shape compound technology is then subtracted using rotational gravity, use
Primary vacuum drying molding, ball particle shape is prepared by presintering material, and presintering material each component is made to reach uniformly mixing and cause
Form of spherical particles presintering material is placed in inert atmosphere sintering furnace by close effect, through 600~800 DEG C of calcining a few hours, with stove
Cooling simultaneously obtains lithium iron phosphate positive material after crushing, sieving；The lithium source is lithium carbonate, lithium hydroxide, lithium oxalate
In one or more, source of iron uses di(2-ethylhexyl)phosphate using the one or more in ferrous oxalate or iron oxide, phosphorus source
One or more in hydrogen ammonium, diammonium hydrogen phosphate, five three phosphorus of oxidation, the doped source substance are acetylene black, conductive charcoal
The mixture of one or more of black, glucose, epoxy resin, phenolic resin, polyethylene glycol, metal oxide.It is above-mentioned special
Profit application has that the abrasive material time is longer, and micro doped source substance is more difficult mixed with the larger source of iron of quality accounting, lithium source, carbon source
Close uniform problem.
It is known that battery-level lithium carbonate（Li2CO3）A kind of important inorganic chemical product, be mainly used as preparing lithium from
Sub- cell positive material（Cobalt acid lithium, ternary material, LiFePO4 etc.）Lithium source.Currently, battery-level lithium carbonate requires its Li2CO3
Content >=99.5%, impurity Pb contents<0.0003%, Ca<0.005%.China withLithiumOre is the battery-level lithium carbonate requirement of raw material
Its Mg content<0.008%, require its Mg content by the battery-level lithium carbonate of raw material of brine<0.015%.
In order to make micro doping component equably mix in lithium iron phosphate particles when preparing LiFePO4, the present invention is logical
Cross and rare earth and/or magnesium be compound in the battery-level lithium carbonate for preparing LiFePO4, make lithium carbonate Mg contents be 0.02~
1.73%, content of rare earth is 0.00~3.2%, you can realizes the lithium position of LiFePO4, the Uniform Doped of iron position or multi-component equal
Even doping, to obtain the lithium iron phosphate positive material of excellent electrical properties.That at home and abroad so far there are no is related for above-mentioned technical method
Report.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of the lithium iron phosphate positive material of doping vario-property, existing to solve
More difficult quantitative control when thering is coprecipitation to mix from magnesium to ferric oxalate, and adulterate the compound of a small amount of magnesium or the change of a small amount of rare earth
Close object carry out compounding, mixing when it is more difficult be uniformly mixed, and to compounding, mixing, grind it is more demanding the problems such as.The present invention passes through
Rare earth and/or magnesium are compound in the battery-level lithium carbonate for preparing LiFePO4, the abrasive material time is not only reduced, reduces production
Cost, and the discharge capacity for the lithium iron phosphate positive material being prepared by this method, cycle performance, high rate performance are more excellent
More, application demand is preferably met.
For achieving the above object, the technical solution adopted by the present invention is as follows：
A kind of preparation method of the lithium iron phosphate positive material of doping vario-property, this method are with doped with magnesium or magnesium-doped and dilute
The battery-level lithium carbonate of soil is lithium source, and by lithium source and source of iron, phosphorus source, carbon source dispensing, grinding, drying obtains the phosphoric acid of doping vario-property
Iron lithium precursor, then precursor calcination process is obtained into lithium iron phosphate positive material product.
The battery-level lithium carbonate, Mg contents are 0.06~1.75%, and preferably Mg contents are 0.5~1.3%.
The battery-level lithium carbonate, content of rare earth are 0.00~3.2%, and rare earth element is selected from light rare earth elements Ce, La
Or two kinds of combination.
The battery-level lithium carbonate is as follows（One）Or method（Two）It prepares：
Method（One）：The old halogen that Li contents are 300~6000mg/L is subjected to rich lithium and drops magnesium processing, obtain Li contents be 6.0~
After the chlorination lithium salts richness lithium solution that 38g/L, Mg content are 8~1740mg/L, Ca contents are 1.2~50mg/L, by chlorination lithium salts
Rich lithium solution is warming up to 70~95 DEG C, and Na is added under agitation2CO3Solution finishes Na2CO3Solution continues to be stirred to react
60~130min, finally through synthesizing, being filtered, washed, dry obtained Li2CO3Content be 93.9~99.4%, Mg contents be 0.04~
1.3% battery-level lithium carbonate product.
The above method（One）In, when the synthesis temperature of lithium carbonate is higher, i.e., the temperature of the described chlorination lithium salts richness lithium solution reaches
At 85~95 DEG C, in order to efficiently control the granularity of lithium carbonate product, also to sodium carbonate liquor or chlorine usually before synthetic reaction
Change and polyethylene glycol is added in lithium salts richness lithium solution, the addition of the polyethylene glycol is the 0.2~0.4% of lithium carbonate product weight.
The above method（One）In, the Na2CO3Solution, wherein Na2CO3Content be 200~310g/L, Mg content
For 20~30mg/L, Na in every liter of chlorination lithium salts richness lithium solution2CO3The addition of solution is 1.07~1.17 times of stoichiometry.
The above method（One）In, in order to make lithium carbonate product that there is more preferably performance, can also Na be added2CO3Solution
While the solution of the rare earth containing Hubeiwan is slowly added dropwise into chlorination lithium salts richness lithium solution；The earth solution is rare earth member
One or more inorganic compound solutions in plain Ce, La, Nd also or are one kind or more in rare earth element ce, La, Nd
The solution of organic compound of kind；The content of the earth solution middle rare earth is 5.0~80g/L, and rare earth is in brine LITHIUM BATTERY carbonic acid
Content in lithium product is：0.05~3.2%.
The above method（One）In, as the Li/Ca mass ratio ＜ 4300 of the chlorination lithium salts richness lithium solution, first selectivity is removed
After removing the Ca impurity in solution, Na is added2CO3Solution, specific method are：It is added in chlorination lithium salts richness lithium solution a concentration of
It is 6.5~7.0 that the sodium hydroxide solution of 75~120g/L, which adjusts pH value, is warming up to 30~60 DEG C, then 1.7 stoichiometrically
~2.2 times of addition Na2CO3, 40~60min is reacted, removes in rich lithium solution 70~94% Ca impurity using filter.
Method（Two）：To carry out removal of impurities processing using lithium ore as the lithium sulfate solution of raw material output, obtain Li contents 16~
20~100mg/L of 30g/L, Mg content, 2~4mg/L of Ca contents lithium sulfate scavenging solution after, by temperature be 20~60 DEG C of lithium sulfates
It is 80~90 DEG C, dissolved with the Na of EDTA and polyethylene glycol that temperature, which is added, in scavenging solution under agitation2CO3In solution, sulfuric acid is finished
Lithium scavenging solution continues to be stirred to react 30~60min in 85~97 DEG C, is then filtered, washed, dries obtained Li2CO3Content is
The battery-level lithium carbonate product that 93.1~99.4%, Mg content are 0.02~1.75%；It, will or after obtaining lithium sulfate scavenging solution
Temperature is 20~60 DEG C, dissolved with the Na of EDTA and polyethylene glycol2CO3The lithium sulfate scavenging solution that temperature is 70~90 DEG C is added in solution
In, finish Na2CO3Solution continues to be stirred to react 30~60min in 85~97 DEG C, is then filtered, washed, dries obtained Li2CO3
Content is the battery-level lithium carbonate product that 93.1~99.4%, Mg contents are 0.02~1.75%.
The above method（Two）In, the Na2CO3Solution, wherein Na2CO3Content be 280~300g/L, Mg content
For 10~30mg/L, Na in every liter of lithium sulfate scavenging solution2CO3The addition of solution is 1.1~1.2 times of stoichiometry.
The above method（Two）In, in order to obtain the lower lithium carbonate product of Ca contents, Na2CO3Added with suitable in solution
EDTA.The EDTA and Na2CO3The molar ratio of calcium is 1.5 ﹕, 1~2.5 ﹕ 1 in solution.
The above method（Two）In, it, can also be to lithium sulfate scavenging solution in order to make lithium carbonate product that there is more preferably performance
Or Na2CO3The earth solution of the light rare earth containing Hubeiwan is added dropwise in solution；The earth solution is in rare earth element ce, La
One or more solution of organic compound in one or more inorganic compound solution or rare earth element ce, La；
The content of the earth solution middle rare earth is 5.0~80g/L, and content of the rare earth in battery-level lithium carbonate product is：0.05~
3.2wt%。
The above method（Two）In, in order to obtain the smaller lithium carbonate product of granularity, Na2CO3Added with polyethylene glycol in solution.
The addition of the polyethylene glycol is the 0.2~0.4% of lithium carbonate product weight.
The source of iron is selected from ferrous oxalate or ferric phosphate, preferably ferric phosphate.
When select ferric phosphate for source of iron when, simultaneously also be phosphorus source；When using ferrous oxalate as source of iron, then di(2-ethylhexyl)phosphate is selected
Hydrogen ammonium is as phosphorus source.
To further increase the electrical property of LiFePO4, it usually needs it is binary doped to carry out magnesium, titanium；The present invention is to pass through carbon
Magnesium is doped in LiFePO4 by sour lithium, and titanium is mixed in ferric phosphate in advance with conventional coprecipitation, and the Ti contents of ferric phosphate are
0.15~0.32%.
The carbon source is selected from glucose or sucrose.
The preparation method of the LiFePO4 precursor is：By lithium source, source of iron, phosphorus source, carbon source and doping metals compound
It weighed, mixed, add 3~8h of grinding in high energy ball mill, then the body before 70~80 DEG C of drying LiFePO4s
Body.
The lithium source, source of iron, phosphorus source and doping metals compound are 1.00~1.05 ﹕, 1 ﹕, 1~1.03 ﹕ by Li ﹕ Fe ﹕ P ﹕ M
0.001~0.04 molar ratio mixing, wherein M are doping metals；The carbon source is added by the weight ratio of solid-phase material 6~17%.
82~92% absolute ethyl alcohol of solid-phase material weight can be added in mechanical milling process.
The doping metals M is one or more in Mg, Ce, La, Ti.
The precursor calcination process is：LiFePO4 precursor is placed in box roaster, under nitrogen protection in
660~750 DEG C roast 7~15 hours, cool to 25~50 DEG C with the furnace, come out of the stove, and crush, are sieved, packing up to LiFePO4 just
Pole material product.
Compared with prior art, the present invention has the following advantages and beneficial effects：
1, the doping of LiFePO4, the prior art are used to source of iron（Ferrous oxalate or ferric phosphate）, lithium source（Lithium carbonate or hydrogen-oxygen
Change lithium）The compound for waiting for doped chemical is added in dispensing, or in advance by doped chemical（Such as magnesium）It is compound in source of iron（Such as oxalic acid Asia
Iron）In, also have and titanium co-precipitation is subjected to single doped titanium report in ferric phosphate；But carrying out two or more
When multiple-composite doped spinel, micro doping component is more difficult to be uniformly mixed with primary raw materials such as source of iron, lithium sources.The present invention pass through by
Magnesium or magnesium and rare earth are compound in advance in the lithium carbonate as lithium source, mix magnesium when being not only advantageous to prepare LiFePO4, are mixed dilute
The Uniform Doped of soil or magnesium and rare earth is particularly advantageous for adulterating Mg, Ce, La in the lithium position of LiFePO4.
2, it is uniformly mixed with primary raw material in order to which constituent element will be adulterated, the prior art is to source of iron, lithium source（Such as lithium carbonate）, Mg etc.
Doping component（Such as magnesium acetate）Mixture carry out abrasive material, mixing, the time needed is longer, usually 5~16h；And it is of the invention
Since doping constituent element is compound in lithium source in advance（Lithium carbonate）, source of iron（Ferric phosphate）In, therefore the required abrasive material time is shorter, only
It is more energy saving for 3~5h.
3, the present invention is compound by by Hubeiwan magnesium or magnesium and rare earth, being carried out with lithium carbonate, not only relatively easily realizes
The Uniform Doped of LiFePO4, and lithium iron phosphate positive material obtained has higher discharge capacity for the first time, preferably
Cycle performance and high rate performance, preferably meet application demand.
Specific implementation mode
For the technology contents that the present invention will be described in detail and the technique effect realized, following examples are provided, but implement
Example is not construed as limiting the invention itself.
One, the source of iron arrived involved in following embodiment of the present invention, including：Ferric phosphate, the ferric phosphate of titaniferous, ferrous oxalate,
Their main chemical compositions（Weight percent）Refer to table（One）.
1）With the Fe in hydrogen peroxide oxidation ferrous sulfate solution2+For Fe3+, then ammonium dihydrogen phosphate is added into solution and carries out
Reaction, through being filtered, washed, drying, obtains hypophosphite monohydrate iron（FePO4·2H2O）；Hypophosphite monohydrate iron is forged at 600~650 DEG C
2h is burnt to get ferric phosphate（FePO4）.
2）Titanium is added into ferric phosphate using coprecipitation, obtains the ferric phosphate that Ti content is 0.15~0.32%.Titaniferous
The preparation method of ferric phosphate is：The ferric phosphate containing the crystallization water prepared according to a conventional method is added to the water of phosphoric acid concentration 0.5mol/L
It it is 70~75 DEG C, under liquid-solid ratio 3, stirring condition in temperature, by the titaniferous solution of theoretical amount in solution（Titanyl sulfate is dissolved in few
The solution that amount distilled water obtains）It is slowly added dropwise in ferric phosphate slurries, is stirred to react 2h, then filter, dry.It is mixed obtained
Titanium ferric phosphate calcines 2h in Muffle furnace in 600~650 DEG C, obtains mixing titanium anhydrous iron phosphate.
3）Battery level iron oxalate is commercial product.
Table（One）Main chemical compositions/% of source of iron
Two, the electrical test method of LiFePO4 is in embodiment：
It is 90 by mass ratio：5：5 LiFePO4Powder, conductive agent SP, binder PVDF are dissolved in NMP, and it is 42% that solid content, which is made,
Anode sizing agent, and be coated on aluminium foil, the positive band that thickness is 200 μm be made after 90~115 DEG C of high temperature drying, will just
After pole band is dried in vacuo 8h at 80 DEG C, the positive plate of a diameter of 14mm is made after rolling, being punched.It is just with the pole piece of preparation
Pole, metal lithium sheet are cathode, and Celgard 2400 is diaphragm；With 1moL.L-1LiPF6/ EC+DMC+DEC (1:1:1) it is
Electrolyte is assembled into half-cell in argon gas glove box.Then in the blue electricity in Wuhan（LANDCT2001A types）It is tested in test system
Cycle and multiplying power survey performance.
Embodiment 1
Using the lithium carbonate containing magnesium as lithium source, using ferric phosphate as source of iron, the LiFePO4 of magnesium Uniform Doped is prepared.
Embodiment 1-1
Using the lithium carbonate containing magnesium 0.06% as lithium source, using ferric phosphate as source of iron, the LiFePO4 of magnesium Uniform Doped is prepared
（LiMg0.001Fe0.999PO4/C）.
Take 48.00g ferric phosphates, lithium carbonate, 8.00g glucose and the anhydrous second of 72mL that 11.85g content of magnesium is 0.06%
Above-mentioned material is added in high energy ball mill and grinds 3h by alcohol, in 70 DEG C of drying, is then warming up to 670 DEG C of burnings under nitrogen protection
13h is tied, 25 DEG C is cooled to the furnace, comes out of the stove, is ground up, sieved, packs up to magnesium-doped LiFePO4 product, which is
L-1-1a。
Embodiment 1-2
Using the lithium carbonate containing magnesium 0.65% as lithium source, using ferric phosphate as source of iron, the LiFePO4 of magnesium Uniform Doped is prepared
（LiMg0.01Fe0.99PO4/C）.
Take 48.00g ferric phosphates, lithium carbonate, 8.00g glucose and the anhydrous second of 80mL that 12.27g content of magnesium is 0.65%
Above-mentioned material is added in high energy ball mill and grinds 3h by alcohol, in 80 DEG C of drying, is then warming up to 700 DEG C of burnings under nitrogen protection
10h is tied, 40 DEG C is cooled to the furnace, comes out of the stove, is ground up, sieved, packs up to magnesium-doped LiFePO4 product, which is
L-1-1b。
Embodiment 1-3
Using the lithium carbonate containing magnesium 1.74% as lithium source, using ferric phosphate as source of iron, the LiFePO4 of magnesium Uniform Doped is prepared
（LiMg0.03Fe0.97PO4/C）.
Take 48.00g ferric phosphates, lithium carbonate, 8.00g glucose and the anhydrous second of 80mL that 13.04g content of magnesium is 1.74%
Above-mentioned material is added in high energy ball mill and grinds 4h by alcohol, in 80 DEG C of drying, is then warming up to 720 DEG C of burnings under nitrogen protection
8h is tied, 50 DEG C is cooled to the furnace, comes out of the stove, is ground up, sieved, packs up to magnesium-doped LiFePO4 product, which is
L-1-1c。
In contrast, the battery-level lithium carbonate for being 0.005% using content of magnesium adds magnesium acetate to adulterate same amount of magnesium as lithium source,
Milling time is 6h, is then synthesized under the conditions of same as embodiment 1-2, and LiFePO4 product is prepared, the product identification
For L-1-2.The battery-level lithium carbonate for being 0.005% using content of magnesium under the conditions of same as embodiment 1-2, undopes as lithium source
Magnesium prepares LiFePO4 product, which is L-1-3.The electric performance test of product is related to the results are shown in Table 1.
1 lithium iron phosphate positive material electrical performance indexes of table compare
Embodiment 2
Using the lithium carbonate containing rare earth as lithium source, using ferric phosphate as source of iron, the LiFePO4 of light rare earth Uniform Doped is prepared.
Embodiment 2-1
The lithium carbonate for being 0.36% using lanthanum content is lithium source, using ferric phosphate as source of iron, prepares the LiFePO4 of lanthanum Uniform Doped
（Li0.997La0.001FePO4/C）.
Take 48.00g ferric phosphates, lithium carbonate, 12.00g glucose and the anhydrous second of 80mL that 11.92g lanthanum contents are 0.36%
Above-mentioned material is added in high energy ball mill and grinds 4h by alcohol, in 80 DEG C of drying, is then warming up to 680 DEG C of burnings under nitrogen protection
13h is tied, 30 DEG C is cooled to the furnace, comes out of the stove, is ground up, sieved, packs the LiFePO4 product of doped lanthanum to obtain the final product, which is
L-2-1。
Embodiment 2-2
Using the lithium carbonate containing lanthanum 1.75% as lithium source, using ferric phosphate as source of iron, the LiFePO4 of magnesium Uniform Doped is prepared
（Li0.985La0.005FePO4/C）.
Take 48.00g ferric phosphates, lithium carbonate, 8.00g glucose and the 80mL absolute ethyl alcohols that 11.97g lanthanum contents are 1.75%,
Above-mentioned material is added in high energy ball mill and grinds 3h, in 80 DEG C of drying, is then warming up to 700 DEG C of sintering under nitrogen protection
10h cools to 40 DEG C with the furnace, comes out of the stove, and is ground up, sieved, packs the LiFePO4 product of doped lanthanum to obtain the final product, which is L-
2-2。
Embodiment 2-3
Using the lithium carbonate containing cerium 0.08% as lithium source, using ferric phosphate as source of iron, the LiFePO4 of cerium Uniform Doped is prepared
（Li0.9994Ce0.0002FePO4/C）.
Take 48.00g ferric phosphates, lithium carbonate, 8.00g glucose and the 80mL absolute ethyl alcohols that 12.10g cerium contents are 0.08%,
Above-mentioned material is added in high energy ball mill and grinds 3h, in 80 DEG C of drying, is then warming up to 750 DEG C of sintering under nitrogen protection
7h cools to 25 DEG C with the furnace, comes out of the stove, and is ground up, sieved, packs up to the LiFePO4 product of cerium is adulterated, which is L-
2-3。
In contrast, the battery-level lithium carbonate for being 0.005% using content of magnesium adds the same amount of lanthanum of oxalic acid La doped as lithium source,
Milling time is 6h, is then synthesized under the conditions of same as embodiment 2-1, and LiFePO4 product is prepared, the product identification
For L-2-4.The electric performance test of product is related to the results are shown in Table 2.
Table 2 mixes the lithium iron phosphate positive material electrical performance indexes comparison of rare earth
Embodiment 3
Using the lithium carbonate containing magnesium 0.63% as lithium source, using the ferric phosphate of titaniferous 0.32% as source of iron, the composite mixed phosphorus of magnesium, titanium is prepared
Sour iron lithium anode material（Li0.98Mg0.01Fe0.98Ti0.01PO4/C）.
Take 48.00g ferric phosphates, lithium carbonate, 8.50g glucose and the 80mL absolute ethyl alcohols that 12.17g content of magnesium is 0.63%,
Above-mentioned material is added in high energy ball mill and grinds 4h, in 80 DEG C of drying, is then warming up to 680 DEG C of sintering under nitrogen protection
12h cools to 35 DEG C with the furnace, comes out of the stove, and is ground up, sieved, packs up to magnesium-doped, titanium LiFePO4 product, the product identification
For L-3-1.
In contrast, add magnesium acetate magnesium-doped, metatitanic acid fourth fat is added to mix titanium, prepare the composite mixed LiFePO4 of magnesium, titanium
Positive electrode（Mg, Ti content are identical as preceding sample）.The product identification is L-3-2.The electric performance test of product the results are shown in Table 3.
3 lithium iron phosphate positive material electrical performance indexes of table compare
Embodiment 4
Using containing magnesium 0.55%, the lithium carbonate containing cerium 0.37% as lithium source, using the ferric phosphate of titaniferous 0.32% as source of iron, prepare magnesium, cerium,
The composite mixed lithium iron phosphate positive material of titanium.
Take 48.00g ferric phosphates, 12.34g containing magnesium 0.55%, the lithium carbonate containing cerium 0.37%, 8.50g glucose and 85mL without
Above-mentioned material is added in high energy ball mill and grinds 3h by water-ethanol, in 80 DEG C of drying, is then warming up to 660 under nitrogen protection
DEG C sintering 15h, cools to 30 DEG C with the furnace, comes out of the stove, be ground up, sieved, pack up to magnesium-doped, titanium LiFePO4 product, the production
Product number is L-4-1.
In contrast, add magnesium acetate to mix magnesium, cerium oxalate is added to mix cerium, metatitanic acid fourth fat is added to mix titanium, prepare that magnesium, cerium, titanium are compound to be mixed
Miscellaneous LiFePO4（The product that the content of Mg, Ce, Ti are L-4-1 with number）Positive electrode, the product identification are L-4-2.Production
The electric performance test of product the results are shown in Table 4.
4 lithium iron phosphate positive material electrical performance indexes of table compare
Embodiment 5
It is phosphorus source by source of iron, ammonium dihydrogen phosphate of ferric oxalate using the lithium carbonate containing magnesium 0.63% as lithium source, prepares magnesium Uniform Doped
LiFePO4（LiMg0.01Fe0.99PO4/C）.
Embodiment 5-1
Take 48.00g ferric oxalates, 10.74g content of magnesium be 0.63% lithium carbonate, 31.21g ammonium dihydrogen phosphates, 6.00g glucose and
Above-mentioned material is added in high energy ball mill and grinds 4h by 80mL absolute ethyl alcohols, in 80 DEG C of drying, then heats up under nitrogen protection
To 400 DEG C of calcining 6h, then 750 DEG C of sintering 12h are warming up to, cool to 50 DEG C with the furnace, come out of the stove, is ground up, sieved, packs up to adulterating
The LiFePO4 product of magnesium, titanium, the product identification are L-5-1.
Embodiment 5-2
Take the lithium carbonate, 31.21g ammonium dihydrogen phosphates, 6.00g glucose that 48.00g ferric oxalates, 10.74g content of magnesium are 0.63%
And 80mL absolute ethyl alcohols, above-mentioned material is added in high energy ball mill and grinds 4h, in 75 DEG C of drying, is then risen under nitrogen protection
Temperature is to 450 DEG C of calcining 3h, then is warming up to 700 DEG C of sintering 16h, cools to 25 DEG C with the furnace, comes out of the stove, is ground up, sieved, packs and mix to obtain the final product
The LiFePO4 product of miscellaneous magnesium, titanium, the product identification are L-5-2.
In contrast, the battery-level lithium carbonate for being 0.005% using content of magnesium adds magnesium acetate to adulterate same amount of magnesium as lithium source,
Milling time is 6h, is then synthesized under the conditions of being L-5-2 same with product identification, the magnesium-doped LiFePO4 production of output
Product, the product identification are L-5-3.The electric performance test of product the results are shown in Table 5.
5 lithium iron phosphate positive material electrical performance indexes of table compare
It can be seen that from the electric performance test result in table 1-5 and made with the battery-level lithium carbonate for being compounded with magnesium and/or rare earth in advance
For lithium source, and with source of iron, phosphorus source, carbon source dispensing, the lithium iron phosphate positive material prepared, relative to conventional batteries grade carbonic acid
Lithium is lithium source, and the acylate of magnesium is used in dispensing（Ethanedioic acid magnesium etc.）, inorganic acid salt（Such as magnesium nitrate）Or the oxalic acid of rare earth
The lithium iron phosphate positive material that salt is prepared as dopant, 0.1C discharge performances, 1C discharge performances are all more excellent, while 1C is followed
The discharge performance that ring 10 times, 1C recycle 30 times is also more excellent.
Claims (10)
1. a kind of preparation method of the lithium iron phosphate positive material of doping vario-property, it is characterised in that：With doped with magnesium or magnesium-doped
Battery-level lithium carbonate with rare earth is lithium source, and by lithium source and source of iron, phosphorus source, carbon source dispensing, grinding, drying obtains doping vario-property
LiFePO4 precursor, then precursor calcination process is obtained into lithium iron phosphate positive material product.
2. a kind of preparation method of the lithium iron phosphate positive material of doping vario-property according to claim 1, it is characterised in that：
The battery-level lithium carbonate, Mg contents are 0.06~1.75%.
3. a kind of preparation method of the lithium iron phosphate positive material of doping vario-property according to claim 1, it is characterised in that：
The battery-level lithium carbonate, content of rare earth are 0.05~3.2%, and rare earth element is selected from light rare earth elements Ce, La or two kinds
Combination.
4. a kind of preparation method of the lithium iron phosphate positive material of doping vario-property according to claim 1, it is characterised in that：
The preparation method of the LiFePO4 precursor is：Lithium source, source of iron, phosphorus source, carbon source and doping metals compound are weighed,
Mixing adds 3~8h of grinding in high energy ball mill, then in 70~80 DEG C of drying LiFePO4 precursors.
5. according to a kind of preparation method of the lithium iron phosphate positive material of doping vario-property described in claim 3, feature exists
In：The lithium source, source of iron, phosphorus source and doping metals compound are 1.00~1.05 ﹕, 1 ﹕, 1~1.03 ﹕ 0.001 by Li ﹕ Fe ﹕ P ﹕ M
~0.04 molar ratio mixing, wherein M are doping metals；The carbon source is added by the weight ratio of solid-phase material 6~17%.
6. a kind of preparation method of the lithium iron phosphate positive material of doping vario-property according to claim 5, it is characterised in that：
The doping metals M is one or more in Mg, Ce, La, Ti.
7. according to a kind of preparation method of the lithium iron phosphate positive material of doping vario-property described in claim 1, feature exists
In：The precursor calcination process is：LiFePO4 precursor is placed in box roaster, under nitrogen protection in 660~
750 DEG C are sintered 7~15 hours, cool to 25~50 DEG C with the furnace, come out of the stove, and crush, are sieved, packing up to lithium iron phosphate positive material
Product.
8. according to a kind of preparation method of the lithium iron phosphate positive material of doping vario-property described in claim 1, feature exists
In：The source of iron is selected from ferric phosphate or ferrous oxalate.
9. a kind of preparation method of the lithium iron phosphate positive material of doping vario-property according to claim 1 or 8, feature exist
In：When the source of iron is ferrous oxalate, select ammonium dihydrogen phosphate as phosphorus source.
10. according to a kind of preparation method of the lithium iron phosphate positive material of doping vario-property described in claim 8, feature exists
In：Titanium is mixed in the ferric phosphate, the Ti contents of ferric phosphate are 0.15~0.32%.
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| CN113086995A (en) * | 2021-03-09 | 2021-07-09 | 北京当升材料科技股份有限公司 | Lithium salt and positive electrode material, and preparation method and application thereof |
| CN114400395A (en) * | 2022-02-22 | 2022-04-26 | 楚能新能源股份有限公司 | Method for preparing lithium cobalt phosphate by recycling waste lithium cobalt oxide |
| CN114566393A (en) * | 2022-03-23 | 2022-05-31 | 上海奥威科技开发有限公司 | Composite positive electrode material for lithium ion capacitor and application thereof |
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