CN100537420C - Method for preparing anode material of lithium ion battery in series of phosphate of olivine type - Google Patents
Method for preparing anode material of lithium ion battery in series of phosphate of olivine type Download PDFInfo
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- CN100537420C CN100537420C CNB2007100349402A CN200710034940A CN100537420C CN 100537420 C CN100537420 C CN 100537420C CN B2007100349402 A CNB2007100349402 A CN B2007100349402A CN 200710034940 A CN200710034940 A CN 200710034940A CN 100537420 C CN100537420 C CN 100537420C
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Abstract
This invention relates to a method for preparing olivine-type phosphate-series lithium ion battery anode material. The method comprises: mixing one or more of ferrous salt solution, cobalt salt solution and manganese salt solution with oxalic acid or oxalate (precipitating agent) aqueous solution to obtain composite oxalate precursor, uniformly mixing with lithium source and phosphorus source by ball milling, and reacting in inert or weak-reductive atmosphere to obtain olivine-type phosphate-series lithium ion battery anode material. The method utilizes co-precipitation method for metal ion doping, and realizes molecular level uniform mixing among different ions. The obtained olivine-type phosphate-series lithium ion battery anode material has uniform chemical and physical compositions. The average particle size can be controlled within 0.3-10 mu.m. The first charge and discharge cycle specific capacity can reach 150 mAh/g at 0.1 C rate and room temperature. The livine-type phosphate-series lithium ion battery anode material has such advantages as high cycle performance and high charge/discharge performance.
Description
Technical field
The present invention relates to a kind ofly carry out the preparation method of the anode material of lithium ion battery in series of phosphate of olivine type of metal ion mixing, belong to technical field of material by coprecipitation method.
Background technology
In recent years, the research and development of lithium ion battery has obtained gratifying achievement, particularly the exploitation of the improvement of negative pole performance and electrolyte system has obtained very big achievement, but the research of anode material for lithium-ion batteries seems and relatively lags behind, and has become the bottleneck that restriction lithium ion battery market and Application Areas are expanded.Serial positive electrode materials such as cobalt acid lithium, lithium nickelate, lithium/nickel/cobalt composite oxide, lithium manganate, lithium vanadate are the focuses of positive electrode material research field research always.The lithium cobaltate cathode material that generally uses in the present commercialization lithium ion battery, though have theoretical capacity and the excellent cycle performance of 274mAh/g, actual capacity has only about 140mAh/g, and the cobalt resource scarcity, costs an arm and a leg.Though the lithium nickelate actual capacity can reach about 200mAh/g, in actual charge and discharge process, easily undergoes phase transition when being nonstoichiometry, influence material stable circulation performance, and the oxygen that decomposites may react poor safety performance with electrolytic solution.Though the Application and Development of lithium manganate having spinel structure can solve the price problem of cobalt acid lithium and the safety problem of lithium nickelate, its capacity is not high and high temperature stability performance is poor.
Since late 1990s, the lithium ion of olivine-type lithium iron phosphate positive material has taken off since the embedding performance reported, LiFePO
4The performance of positive electrode material and study on the modification thereof become the new focus of battery circle research.Olivine-type LiFePO
4Belong to rhombic system, spacer is Pnma, and theoretical capacity is 170mAh/g, and discharge voltage plateau is 3.4V (Li
+/ Li), crystalline structure does not change before and after the discharge fully, and volume only changes 6.81%, has good cycle performance and safety performance, and raw material sources are abundant, environmental friendliness.LiFePO
4Positive electrode material with the obvious advantage, but shortcoming is very important equally.At first, LiFePO
4True density be starkly lower than LiCoO
2, LiNiO
2And LiMn
2O
4Deng positive electrode material, will inevitably influence the energy density of battery, influence the processing characteristics in the material pole piece preparation process simultaneously; Secondly, LiFePO
4During positive electrode material is synthetic, Fe
2+Easily be oxidized to Fe
3+, be difficult for making pure phase LiFePO
4Positive electrode material; Once more, because LiFePO
4Self structure limits, and causes its ion and electronic conductivity not good, and this has become the maximum bottleneck of its development of restriction and application.
At LiFePO
4These problems that positive electrode material exists mainly concentrate on following three aspects to its study on the modification at present: optimize synthesis technique, add electro-conductive material and doped metal ion.
By optimizing synthesis technique, seek appropriate preparation method and control condition, can improve LiFePO
4The pattern of positive electrode material, globule size, density, purity and apparent conductivity.Present LiFePO
4The preparation method mainly contain solid phase method, the precipitator method, hydrothermal method, colloidal sol-gel, microwave method etc.Adding conductivity favorable conductive carbon or carbon compound, metal or metal oxide etc., is to improve LiFePO
4An effective way of apparent conductivity.Add carbon, not only can the refinement particle, improve the conductivity of material, can also suppress Fe as reductive agent
2+Oxidation, but, will inevitably influence the energy density of positive electrode material because the density of carbon is little.Add metals such as super fine silver powder or copper powder and can improve the conductivity of material, and do not influence the material energy density, but can't suppress Fe
2+Oxidation, and cost is higher.Optimize synthesis technique, add the apparent conductivity that electro-conductive material can only improve material, for improving the intrinsic conduction performance of material, LiFePO
4Li position and Fe position doping little metal ion, it is a kind of feasible method, the mode of doped metal ion mainly is that the principal element compound is directly mixed with ball mill with doping element compound at present, it is synthetic to carry out high temperature sintering then, and this method is difficult to prepare the metal ion mixing lithium iron phosphate positive material that mixes.
Summary of the invention
At the deficiency of aforesaid method and means, the invention provides that a kind of technology is simple, with low cost, the preparation method of the metal ion mixing anode material of lithium ion battery in series of phosphate of olivine type that is suitable for suitability for industrialized production.
A kind of preparation method of anode material of lithium ion battery in series of phosphate of olivine type may further comprise the steps:
(1) with in solubility divalent iron salt and soluble transition metal nickel salt, cobalt salt or the manganese salt one or more by required Fe/M (M=Ni, Co, Mn, Ni+Mn, Ni+Co, Mn+Co, Ni+Co+Mn) mol ratio is mixed with the solution of 0.1～3.0mol/L, the precipitation agent oxalic acid or the oxalate solution that in closed reaction vessel, slowly add 0.1～2.0mol/L, 30～90 ℃ of temperature of reaction, with the ammonia soln of 2.0～8.0mol/L and the acid solution conditioned reaction pH of 0.5～2.0mol/L, when the pH value is 0.2～4.0, make compound oxalate precursor A.
(2) two or three in nickel salt, cobalt salt or the manganese salt (Ni+Co, Ni+Mn, Mn+Co, Ni+Co+Mn) is mixed with the mixing solutions of 0.1～3.0mol/L by required mol ratio, the precipitation agent oxalic acid or the oxalate solution that in closed reaction vessel, slowly add 0.1～2.0mol/L, 30～90 ℃ of temperature of reaction, with the ammonia soln of 2.0～8.0mol/L and the acid solution conditioned reaction pH of 0.5～2.0mol/L, when the pH value is 6.0～12.0, make compound oxalate precursor B.
(3) mixture with precursor A or precursor B or precursor A and B mixed with lithium source, phosphorus source in 1: 0.91 in molar ratio～1.09: 1, added the dehydrated alcohol mixing and ball milling 1～5 hour, under inertia or weak reducing atmosphere, 300～450 ℃ of constant temperature pre-treatment 3～8 hours are warming up to 500～800 ℃ of high-temperature heat treatment and obtained anode material of lithium ion battery in series of phosphate of olivine type in 5～30 hours.
Described solubility divalent iron salt can be selected iron protochloride, ferrous sulfate, ferrous ammonium sulphate, Iron nitrate or Iron diacetate for use.
Described soluble transition metal nickel, cobalt, manganese salt can be selected muriate, vitriol, nitrate or the acetate of nickel, cobalt, manganese for use.
Described precipitation agent and metal ion mol ratio are: N
C2042-: N
M2+(transition metal ion summation) is 0.8～1.5.
Described oxalate comprises ammonium oxalate or sodium oxalate.
Described lithium source can be selected Quilonum Retard, lithium oxalate, Lithium Acetate, lithium hydroxide, lithium chloride, lithium nitrate or Lithium Sulphate for use.
Described phosphorus source can be selected primary ammonium phosphate, Secondary ammonium phosphate, triammonium phosphate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, tertiary sodium phosphate, potassium primary phosphate, dipotassium hydrogen phosphate, Tripotassium phosphate for use.
Used inertia or weak reducing atmosphere are selected from a kind of in nitrogen, argon gas and hydrogen and nitrogen mixture or hydrogen and the argon gas gas mixture respectively.
The present invention has following characteristics: (1) adopts coprecipitation method to mix, and has realized principal element and doped element mixing in the atom level level; (2) the product Chemical Composition be evenly distributed, thing phase homogeneous, reaction conditions is controlled; (3) preparation technology is simple, easy to control, the industrial production of easily magnifying; (4) granularity of product and chemical property can be controlled by changing processing condition.Can prepare particle diameter first discharge specific capacity 150mAh/g, anode material of lithium ion battery in series of phosphate of olivine type that cycle performance is good under 0.3～10 μ m, room temperature with this method.
Description of drawings
Fig. 1 embodiment 1 obtained compound oxalate (Fe
0.8Ni
0.2C
2O
4NH
2O) XRD figure of presoma;
Fig. 2 embodiment 1 prepared compound oxalate (Fe
0.8Ni
0.2C
2O
4NH
2O) SEM of presoma figure;
The XRD figure of the lithium iron phosphate positive material of Fig. 3 embodiment 3 prepared doping divalent metal nickel ions;
The SEM figure of the lithium iron phosphate positive material of Fig. 4 embodiment 3 prepared doping divalent metal nickel ions;
The SEM figure of the lithium iron phosphate positive material of Fig. 5 embodiment 4 prepared doping metals nickel ions;
First charge-discharge graphic representation during the lithium iron phosphate positive material room temperature 0.1C of Fig. 6 embodiment 5 prepared doping nickelous manganese metal ions;
The lithium iron phosphate positive material room temperature 0.5C and the 1C charge and discharge cycles capacity plan of Fig. 7 embodiment 5 prepared doping nickelous manganese metal ions.
Embodiment
Embodiment 1
(wherein the mol ratio of iron and nickel is: N with the oxalic acid solution of 1.0mol/L and the ferrous sulfate of 0.8mol/L and the mixing solutions of single nickel salt
Fe2+: N
Ni2+=4: 1) mix, 50 ℃ of control reaction temperature, pH value in reaction 2.0 makes compound oxalate precipitation, after filtration, the washing drying, allocates stoichiometric ratio NH into
4H
2PO
4And Li
2CO
3, adding an amount of dehydrated alcohol ball milling 5h on ball mill, oven dry obtains sample.Sample is changed in the confined reaction stove, under the argon gas atmosphere protection, in 380 ℃ of decomposition 5h, be warming up to 600 ℃, calcination 20h cools to room temperature then with the furnace again.Products therefrom is indicated as rhombic system olivine-type iron lithium phosphate through X-ray diffraction analysis, and crystalline structure is complete.
With total concn (Fe+Ni) is 0.8mol/L, different Fe
2+With Ni
2+The mixing solutions of mol ratio mixes with the oxalic acid solution of 1.2mol/L, and pH value in reaction 2.0,50 ℃ of temperature of reaction, reaction gained precipitation are after filtration, after the washing, drying, allocate an amount of NH into according to stoichiometric ratio
4H
2PO
4, Li
2CO
3, ball milling 5h in ethanol medium.After the screening of ball milling compound sample drying, change in the confined reaction stove, under the argon gas atmosphere protection,, be warming up to 600 ℃ of calcination 20h, cool to room temperature then with the furnace in 380 ℃ of thermolysis 5h.Products therefrom is assembled into Experimental cell, with its first discharge specific capacity of constant current charge-discharge technical measurement, carries out constant-current discharge at the 0.1C discharging current, their first discharge specific capacity is as shown in table 1.
Table 1 is mixed the influence of nickel amount to the lithium iron phosphate positive material loading capacity
With total concn (Fe+Ni) is 0.8mol/L, Fe
2+With Ni
2+Mol ratio is: N
Fe2+: N
Ni2+=0.95: 0.05 mixing solutions mixes with the oxalic acid solution of 1.2mol/L, and control pH value in reaction 2.0,50 ℃ of temperature of reaction, reaction gained precipitation are after filtration, after the washing, drying, allocate an amount of NH into according to stoichiometric ratio
4H
2PO
4, Li
2CO
3, ball milling 5h in ethanol medium.After the screening of ball milling compound sample drying, change in the confined reaction stove, under the argon gas atmosphere protection,, be warming up to 600 ℃ of calcination 20h, cool to room temperature then with the furnace at different pretreatment temperature thermolysis 5h.Products therefrom is assembled into Experimental cell, with its first discharge specific capacity of constant current charge-discharge technical measurement, carries out constant-current discharge at the 0.1C discharging current, their first discharge specific capacity is as shown in table 2.
The different pretreatment temperature gained of table 2 are mixed nickel lithium iron phosphate positive material specific discharge capacity
With total concn (Fe+Ni) is 0.8mol/L, Fe
2+With Ni
2+Mol ratio is: N
Fe2+: N
Ni2+=0.95: 0.05 mixing solutions mixes with the oxalic acid solution of 1.2mol/L, and control pH value in reaction 2.0,50 ℃ of temperature of reaction, reaction gained precipitation are after filtration, after the washing, drying, allocate an amount of NH into according to stoichiometric ratio
4H
2PO
4, Li
2CO
3, ball milling 5h in ethanol medium.After the screening of ball milling compound sample drying, change in the confined reaction stove, under the argon gas atmosphere protection, 380 ℃ of thermolysis 5h are warming up to temperature required calcination 20h, cool to room temperature then with the furnace.Products therefrom is assembled into Experimental cell, with its first discharge specific capacity of constant current charge-discharge technical measurement, carries out constant-current discharge at the 0.1C discharging current, their first discharge specific capacity is as shown in table 3.
The different synthesis temperature gained of table 3 are mixed nickel lithium iron phosphate positive material specific discharge capacity
With total concn (Fe+Ni) is 0.8mol/L, Fe
2+With Ni
2+Mol ratio is: N
Fe2+: N
Ni2+=0.95: 0.05 mixing solutions mixes with the oxalic acid solution of 1.2mol/L, and control pH value in reaction 2.0,50 ℃ of temperature of reaction, reaction gained precipitation are after filtration, after the washing, drying, allocate an amount of NH into according to stoichiometric ratio
4H
2PO
4, Li
2CO
3, ball milling 5h in ethanol medium.After the screening of ball milling compound sample drying, change in the confined reaction stove, under the argon gas atmosphere protection, 380 ℃ of thermolysis 5h are warming up to 650 ℃ of calcination different times, cool to room temperature then with the furnace.Products therefrom is assembled into Experimental cell, with its first discharge specific capacity of constant current charge-discharge technical measurement, carries out constant-current discharge at the 0.1C discharging current, their first discharge specific capacity is as shown in table 4.
The different generated time gained of table 4 are mixed nickel lithium iron phosphate positive material specific discharge capacity
Embodiment 6
The ferrous iron solution of 0.8mol/L is mixed with the oxalic acid solution of 1.2mol/L, control pH value in reaction 2.0,50 ℃ of temperature of reaction make yellow Ferrox presoma; According to Mn
2+With Ni
2+Mol ratio be: N
Mn2+: N
Ni2+Be mixed with mixing solutions that total concn be 0.8mol/L at=1: 1, this mixing solutions is mixed with the oxalic acid solution of 1.2mol/L, and control pH value in reaction 8.2,60 ℃ of temperature of reaction make brown compound oxalate presoma; Ferrox presoma, compound oxalate presoma are pressed N
Fe2+: N
Mn2+: N
Ni2+=0.90: 0.05: 0.05 mol ratio and stoichiometric ratio Li
2CO
3And NH
4H
2PO
4Mix ball milling 5h in ethanol medium.After the screening of ball milling compound sample drying, change in the confined reaction stove, under the argon gas atmosphere protection,, be warming up to 650 ℃ of calcination 20h, cool to room temperature then with the furnace in 380 ℃ of thermolysis 5h.Products therefrom is assembled into Experimental cell, with its first discharge specific capacity of constant current charge-discharge technical measurement, carries out constant-current discharge at the 0.1C discharging current, its first charge-discharge capacity is respectively 156.7 and 150mAh/g, but coulomb reverse efficiency 95.7% first; When 0.5C and 1C discharged and recharged, through 50 circulations, specific discharge capacity was respectively 121.2mAh/g and 104.4mAh/g, shows higher electrochemistry capacitance and excellent cycle performance (see figure 7).
Claims (7)
1. the preparation method of an anode material of lithium ion battery in series of phosphate of olivine type is characterized in that: may further comprise the steps:
(1) solubility divalent iron salt and soluble transition metal M salt are mixed with the solution of 0.1～3.0mol/L by required Fe/M mol ratio, the precipitation agent oxalic acid or the oxalate solution that in closed reaction vessel, slowly add 0.1～2.0mol/L, 30～90 ℃ of temperature of reaction, regulating the pH value is 0.2～4.0, makes compound oxalate precursor A; Described transition metal M salt is one or more in nickel salt, cobalt salt or the manganese salt;
(2) precursor A was mixed with lithium source, phosphorus source in 1: 0.91 in molar ratio～1.09: 1, added the dehydrated alcohol mixing and ball milling 1～5 hour, under inertia or weak reducing atmosphere, 300～450 ℃ of constant temperature pre-treatment 3～8 hours are warming up to 500～800 ℃ of high-temperature heat treatment and obtained anode material of lithium ion battery in series of phosphate of olivine type in 5～30 hours; Used inertia or weak reducing atmosphere are selected from a kind of in nitrogen, argon gas and hydrogen and nitrogen mixture or hydrogen and the argon gas gas mixture respectively;
Described precipitation agent and metal ion mol ratio are 0.8～1.5.
2. preparation method according to claim 1 is characterized in that: described solubility divalent iron salt is selected iron protochloride, ferrous sulfate, ferrous ammonium sulphate, Iron nitrate or Iron diacetate for use.
3. preparation method according to claim 1 is characterized in that: described transition metal M salt is selected muriate, vitriol, nitrate or the acetate of nickel, cobalt or manganese for use.
4. preparation method according to claim 1 is characterized in that: described oxalate comprises ammonium oxalate or sodium oxalate.
5. preparation method according to claim 1 is characterized in that: described lithium source is selected Quilonum Retard, lithium oxalate, Lithium Acetate, lithium hydroxide, lithium chloride, lithium nitrate or Lithium Sulphate for use.
6. preparation method according to claim 1 is characterized in that: described phosphorus source is selected primary ammonium phosphate, Secondary ammonium phosphate, triammonium phosphate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, tertiary sodium phosphate, potassium primary phosphate, dipotassium hydrogen phosphate or Tripotassium phosphate for use.
7. preparation method according to claim 1 is characterized in that: with the pH of the acid solution conditioned reaction system of the ammonia soln of 2.0～8.0mol/L and 0.5～2.0mol/L.
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