CN103346317B - Composite mixed and cladded type anode material for lithium-ion batteries LiFePO 4and preparation method thereof - Google Patents
Composite mixed and cladded type anode material for lithium-ion batteries LiFePO 4and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of composite mixed and cladded type anode material for lithium-ion batteries LiFePO
4preparation method, comprise the following steps: purchase as the lithium source of raw material, source of iron, phosphorus source and containing doped metallic elements compound, doping metals comprises Nb, Mg, Ti, Mn and Zn; Mixing making beating, drying are carried out to raw material, obtains powdery precursor; The powdery precursor obtained is carried out pre-burning; Second batch and ball-milling treatment are carried out to the product after pre-burning, the compound obtained is sintered, obtain anode material for lithium-ion batteries LiFePO
4.The anode material for lithium-ion batteries LiFePO that the present invention obtains
4middle mixing and doping has five kinds of metallic elements, D
50at 1 ~ 2 μm, specific area is at 16 ~ 21.5m
2/ g, tap density>=1.5g/cm
3.Technique of the present invention is simple and easy to control, production cost is low, the product composition that the present invention obtains evenly, physical and chemical performance and electrical property all excellent.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and preparation thereof, particularly relate to a kind of doped modified lithium ion battery anode material LiFePO
4and preparation method thereof.
Background technology
Lithium ion battery is since commercialization, and positive electrode is the study hotspot of field of batteries all the time.A large amount of anode material for lithium-ion batteries used remains LiCoO at present
2but, due to Co scarcity of resources on the earth, cause LiCoO
2expensive.Meanwhile, LiCoO
2also there is obvious defect, mainly thermal stability and overcharging resisting poor-performing, actual specific capacity is on the low side.In addition, LiCoO
2also there is hidden danger at secure context, people are finding other suitable substitution material.In recent years, also developed LiNiO
2, LiMnO
2and LiMn
2o
4deng positive electrode, but all there is certain defect in these materials.Although nickel is than cobalt rich reserves, cheap, LiNiO
2synthesis condition harsh, structural instability, easily generates Li
1-yni
1+yo
2, make part of nickel be arranged in lithium layer, reduce diffusion rate and the cycle performance of lithium ion.The LiMnO of stratiform
2because the unsteadiness on thermodynamics causes its preparation difficulty, and can be converted into spinel structure in the structure of cyclic process laminate, capacity attenuation is very serious.Although the LiMn of spinel structure
2o
4there is the features such as higher operating voltage, cheap, environmental friendliness, but in commercial applications process, LiMn
2o
4following problems are also had to wait to solve: (1) Reversible Cycle capacity is on the low side, is about 115mAh/g; (2) under high temperature, capacitance loss is serious.
First LiFePO is proposed from A.K.Padhi in 1997 etc.
4since can be used as anode material for lithium-ion batteries, due to this material there is low price, nontoxic, Environmental compatibility good, aboundresources, higher specific capacity (theoretical specific capacity 170mAh/g) and higher operating voltage (3.4V, take lithium metal as negative pole), discharge and recharge flatten delay, have extended cycle life, high-temperature behavior and advantage, the LiFePO such as security performance is good
4material has become the focus that battery operated person competitively studies, and is expected to the leading material becoming lithium ion battery of future generation.
But, due to LiFePO
4the restriction of self structure, its poorly conductive and lithium ion diffusion coefficient low, and poorly conductive affects LiFePO
4the main cause of application.Through years of researches, conductivity can be improved about 8 times, and material specific capacity is close to theoretical value by doping, high-rate charge-discharge capability also obtains some improvement simultaneously, inhibits capacity attenuation to a certain extent.In addition, the lattice by dopant activation, improves lithium ion diffusion coefficient.
The study on the modification of existing LiFePO4 mainly comprises the following aspects:
(1) carbon is coated: carbon has excellent electric conductivity and lower mass density, adds a small amount of carbon, can improve the electric conductivity of material, also can reduce the particle diameter yardstick of material in addition.Such as Prosni etc. prepare LiFePO
4/ C compound material, its conductivity improves about 1.5 times, and the discharge capacity under 1C reaches 150mAh/g(see Huang Kelong, Wang Zhaoxiang, Liu Suqin, lithium ion battery principle and key technology [M], Beijing: Chemical Industry Press, 2008).Tin etc. compared for the LiFePO prepared by five kinds of carbon sources
4/ C material, find that carbon doping effectively can improve the conductivity of LiFePO4, but acetylene black, flaky graphite are not good selection, adopt carbon black and glucose and as carbon source, the chemical property of product can be made to get a greater increase (see Nagaura T, Tozawak k.Lithium ion rechargeable battery [J] .Batteries Solar Cells, 1990,9:209-210.).
(2) metal ion mixing: be coated on material surface with carbon and just change interparticle conductivity, to LiFePO
4the conductivity of granule interior but affects very micro-.When the size of particle is not enough hour, obtain big current, high power capacity charge-discharge performance still more difficult, the simultaneously content of active principle and energy density in the too high easy reduction electrode of carbon content.Therefore, generally LiFePO is improved by metal ion mixing
4the conductivity of granule interior.When carrying out metal ion mixing, consider from doping position, Li position or the doping of Fe position can be divided into.The identical solid phase method improved that adopts of Liu has prepared the Li that Mg is mixed in Li position
0.98mg
0.02fePO
4sample, a small amount of Mg
2+doped with being beneficial to the pattern and particle diameter that control product, (see Liu Heng, Sun Honggang, Zhou great Li etc., the solid phase method of improvement prepares lithium iron phosphate cell material [J], Sichuan University's journal to obtain stable LiFePO4 compound, 2004,36 (4): 74-77).Test result shows: in material, the relative lithium electrode current potential of the charge and discharge platform of lithium ion is at about 3.5V, and its initial discharge capacity is more than 160mAh/g, and after 50 charge and discharge cycles, capacity only decays 5.5%, and this shows Mg
2+doping significantly improve specific energy and cyclical stability.Fe position doped metal ion mainly contains Ti
4+, Mn
2+deng.Zhong etc. have synthesized LiFePO
4and Li
0.95fe
0.95ti
0.05pO
4positive electrode is (see Zhong M E, Zhou Z T.Preparation of high tap-density LiFePO
4/ C composite cathode materials by carbothermal reduction method using two kinds of Fe3+precursors materials [J] .Chemistry and physics, 2010,119:428-431.), research finds the Ti of doping
4+occupy Li position and Fe position, the initial discharge capacity under 0.1C multiplying power reduces to 3.3V up to the voltage platform of 158mAh/g, 1C by initial 3.4V, and specific capacity remains on original 70%, with LiFePO simultaneously
4compare, titanium doped sample shows good chemical property.A small amount of additive Mn can reduce the polarization of material, improves the high rate performance of material.This is mainly because additive Mn increases LiFePO
4unit cell volume, more be conducive to deviating from of lithium, the doping of manganese result in sintering process and produces crystal structure defects in addition, improve the electron conduction of material, thus make the high rate performance of material have clear improvement (see Padhi A K, Nanjundaswamy K S, Goodenough J B.Phospho-olivines as Positive electrode Mat erials for Rechargeable Lithium Batteries [J] .J Electrochem Soc, 1997,144 (4): 1188.).
But in the past the doped chemical of report was all generally one or two kind of metallic element, seldom had the metallic element relating to more than three kinds, and its cycle performance of LiFePO4 after doping vario-property and high rate performance are difficult to improve simultaneously, and raising degree is also relatively limited.In addition, existing doping vario-property technological operation step is complicated, and cost is high, and the industrial chemicals such as the organic solvent used in technical process, ammonium salt are easily to environment, and the feature of environmental protection of technique also remains to be further improved.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, provides the composite mixed and cladded type anode material for lithium-ion batteries LiFePO that a kind of technique is simple and easy to control, production cost is low
4preparation method, the product composition that this preparation method obtains evenly, physical and chemical performance and electrical property all excellent and be easy to suitability for industrialized production.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of composite mixed and cladded type anode material for lithium-ion batteries LiFePO
4preparation method, comprise the following steps:
(1) purchase as the lithium source of raw material, source of iron, phosphorus source and containing doped metallic elements compound, described doping metals comprises Nb, Mg, Ti, Mn and Zn; Mixing making beating, dry (such as spraying dry or static dry) are carried out to raw material, obtains powdery precursor;
(2) powdery precursor that step (1) obtains is carried out pre-burning;
(3) second batch and ball-milling treatment (Ball-milling Time is preferably 0.5 ~ 4 hour) are carried out to the product after step (2) pre-burning, after ball milling, carry out spraying dry or static dry again;
(4) compound obtained after step (3) is sintered, obtain physical and chemical performance and all excellent composite mixed and cladded type anode material for lithium-ion batteries LiFePO of electrical property
4.
In above-mentioned preparation method, lithium hydroxide, lithium dihydrogen phosphate or lithium carbonate are preferably used in described lithium source, and described source of iron preferably uses ferrous oxalate, and described phosphorus source is preferably with phosphoric acid or lithium dihydrogen phosphate; Described lithium source and the preferred mol ratio n of source of iron (Li)/n (Fe)=0.98 ~ 1.06, described phosphorus source and the preferred mol ratio n of source of iron (P)/n (Fe)=0.98 ~ 1.05.
In above-mentioned preparation method, preferably, the described doping metals Mg element compound that contains comprises basic magnesium carbonate, magnesium acetate, magnesium hydroxide, one or more in magnesium oxalate, the described doping metals Ti element compound that contains comprises titanium dioxide, the described doping metals Mn element compound that contains comprises manganese acetate, basic carbonate manganese, one or more in manganese oxalate, the described doping metals Zn element compound that contains comprises zinc acetate, basic zinc carbonate, one or more in zinc oxalate, the described doping metals Nb element compound that contains comprises niobium pentaoxide and/or niobium oxalate, the total mole number of all doped metallic elements and phosphorus source, the mol ratio in source of iron or lithium source is 0.001 ~ 0.05.
In above-mentioned preparation method, allocate carbon source in the product after described second batch preferably points to pre-burning, the amount of allocating into of carbon source is by 1% ~ 10% of the product quality after pre-burning.Described carbon source preferably use in citric acid, sucrose, glucose, carbon black, soluble starch one or both.
In above-mentioned preparation method, in described step (3) process conditions of pre-burning preferably control be: programming rate 1 DEG C/min ~ 10 DEG C/min, holding temperature 400 DEG C ~ 700 DEG C, temperature retention time 1 ~ 20 hour, cools naturally with stove.
In above-mentioned preparation method, in described step (5) process conditions of sintering preferably control be: programming rate 1 DEG C/min ~ 10 DEG C/min, holding temperature 600 DEG C ~ 900 DEG C, temperature retention time 1 ~ 20 hour, cools naturally with stove.
In above-mentioned preparation method, the mixing pulping process in described step (1) preferably refers to: described phosphorus source is placed in a container, adds containing doped metallic elements compound under the condition constantly stirred; Then continued mechanical stir, and lithium source is added wherein slip, adopt deionized water cooling slip, pour vertical mill into when slurry temperature drops to 30 DEG C ~ 60 DEG C, and add source of iron, continue Vertical Mill 0.5h ~ 4h; Collect slip.
As a total technical conceive, the present invention also provides a kind of above-mentioned preparation method the anode material for lithium-ion batteries LiFePO obtained
4, described anode material for lithium-ion batteries LiFePO
4middle mixing and doping has Nb, Mg, Ti, Mn and Zn five kinds of metallic elements, described anode material for lithium-ion batteries LiFePO
4d
501 μm ~ 2 μm, specific area is at 16m
2/ g ~ 21.5m
2/ g, tap density>=1.5g/cm
3.
Technique scheme of the present invention proposes based on our following research institute: improving LiFePO when metallic element adulterates separately
4chemical property aspect all tool have certain effect; Such as, Mg
2+doping can improve LiFePO
4intrinsic ionic mobility, reduce the lattice mismatch of two-phase compound in charge and discharge process, improve transformation rate and high power charging-discharging capacity; Ti
4+mix and effectively can suppress LiFePO
4the reunion of particle, makes material refinement, increases substantially LiFePO simultaneously
4chemical property, particularly large multiplying power under cycle performance; And Nb
5+as lithium position doped metal ion, more passage can be provided for the diffusive migration of lithium ion; Mn
2+doping can make Mn
2+metal ion infiltrates LiFePO
4granule interior, forms lattice defect, is conducive to Li
+movement, capacity and cycle performance are promoted; And Zn
2+doping make LiFePO
4charge-transfer resistance reduces, and reversibility strengthens, and improves initial capacity and the cycle performance of material.We show in more deep research, after mixing above five kinds of metallic elements and the coated acting in conjunction of carbon simultaneously, crystals can be made to produce special crystal structure defects, effectively improve LiFePO
4the electronic conductivity of/C composite, is conducive to the fast transport of lithium ion, and the starting voltage reducing material charge and discharge platform is poor, reduces the electrode polarization of positive electrode, has increased substantially large current discharging capability and the cycle performance of positive electrode of the present invention.
Compared with prior art, the invention has the advantages that:
(1) the present invention is simultaneously at Li position and Fe position doping Nb, Mg, Ti, Mn and Zn five kinds of metallic elements, make full use of the cooperative effect of Nb, Mg, Ti, Mn and Zn five kinds of doped chemicals, substantially increase cycle performance and the high rate performance of material, obtain physical and chemical performance and all excellent anode material for lithium-ion batteries LiFePO of electrical property
4.
(2) the present invention adopts water as batch mixing medium, avoids the use of organic solvent, reduces costs, and reduces operating risk.
(3) the present invention maintains the uniformity of wet chemical method synthesis presoma, and chemical property is good.
(4) the present invention adds process of lapping between pre-burning and sintering process, improves the tap density of material.
(5) the present invention does not adopt ammonium salt as raw material, avoids the generation of ammonia in roasting process, and whole technical process does not have the generation of other three wastes simultaneously, environmental friendliness.
To sum up, preparation method of the present invention has the features such as technique is simple and easy to control, production cost is low, and product composition evenly, physical and chemical performance and electrical property all excellent, be easy to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the SEM photo of the product that the method for the embodiment of the present invention 1 prepares.
Fig. 2 is the SEM photo of the product that the method for the embodiment of the present invention 2 prepares.
Fig. 3 is the SEM photo of the product that the method for the embodiment of the present invention 3 prepares.
Fig. 4 is the SEM photo of the product that the method for the embodiment of the present invention 4 prepares.
Embodiment
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but protection range not thereby limiting the invention.
Embodiment 1:
One is composite mixed and cladded type anode material for lithium-ion batteries LiFePO of the present invention as shown in Figure 1
4preparation method, comprise the following steps:
(1) raw material is purchased: purchase as the lithium hydroxide of raw material, ferrous oxalate, phosphoric acid and containing doped metallic elements compound, doping metals comprises Nb, Mg, Ti, Mn and Zn; Basic magnesium carbonate, titanium dioxide, manganese acetate, zinc acetate and niobium oxalate is referred to containing doped metallic elements compound; According to Li
0.95nb
0.01fe
0.968mg
0.01ti
0.006mn
0.006zn
0.004pO
4molecular formula prepare burden.Consider the scaling loss in lithium source and phosphorus source in sintering process, lithium source and phosphorus source is needed to have a small amount of having more than needed, therefore mol ratio n (the Li)/n (Fe)=1.04 of lithium source and source of iron, mol ratio n (the P)/n (Fe) of phosphorus source and source of iron is about 1.03;
(2) mixing making beating: phosphorus source is placed in a container, adds containing doped metallic elements compound under the condition constantly stirred; Then continued mechanical stir, and lithium source is added wherein slip, adopt deionized water cooling slip, pour vertical mill into when slurry temperature drops to 50 DEG C, and add source of iron, continue Vertical Mill 2h; Collect slip; Carry out spraying dry, obtain powdery precursor;
(3) pre-burning: the powdery precursor that step (2) obtains is carried out pre-burning, and pre-burning system is: programming rate 3 DEG C/min, holding temperature 650 DEG C, temperature retention time 6 hours, cools naturally with stove;
(4) second batch: second batch and ball-milling treatment are carried out to the product after step (3) pre-burning, second batch allocates carbon source (selecting glucose as carbon source) in the product after pointing to pre-burning, the amount of allocating into of carbon source is by 5% of the product quality after pre-burning, after adding carbon source, compound is carried out to the ball-milling treatment of 2h, carry out spraying dry afterwards;
(5) compound obtained after step (4) is sintered, the process regulation of sintering is: programming rate 3 DEG C/min, holding temperature 760 DEG C, temperature retention time 16 hours, naturally cool with stove, obtain physical and chemical performance and all excellent composite mixed and cladded type anode material for lithium-ion batteries LiFePO of electrical property
4.
Embodiment 2:
One is composite mixed and cladded type anode material for lithium-ion batteries LiFePO of the present invention as shown in Figure 2
4preparation method, comprise the following steps:
(1) raw material is purchased: purchase as the lithium hydroxide of raw material, ferrous oxalate, phosphoric acid and containing doped metallic elements compound, doping metals comprises Nb, Mg, Ti, Mn and Zn; Basic magnesium carbonate, titanium dioxide, manganese acetate, zinc acetate and niobium oxalate is referred to containing doped metallic elements compound; According to Li
0.99nb
0.01fe
0.984mg
0.01ti
0.006mn
0.006zn
0.004pO
4molecular formula prepare burden, consider the scaling loss in lithium source and phosphorus source in sintering process, mol ratio n (the Li)/n (Fe) of lithium source and source of iron is about 1.04, and mol ratio n (the P)/n (Fe) of phosphorus source and source of iron is about 1.03;
(2) mixing making beating: phosphorus source is placed in a container, adds containing doped metallic elements compound under the condition constantly stirred; Then continued mechanical stir, and lithium source is added wherein slip, adopt deionized water cooling slip, pour vertical mill into when slurry temperature drops to 40 DEG C, and add source of iron, continue Vertical Mill 1.5h; Collect slip; Carry out spraying dry, obtain powdery precursor;
(3) pre-burning: the powdery precursor that step (2) obtains is carried out pre-burning, and pre-burning system is: programming rate 2 DEG C/min, holding temperature 640 DEG C, temperature retention time 6 hours, cools naturally with stove;
(4) second batch: second batch and ball-milling treatment are carried out to the product after step (3) pre-burning, second batch allocates carbon source (selecting glucose as carbon source) in the product after pointing to pre-burning, the amount of allocating into of carbon source is by 5% of the product quality after pre-burning, after adding carbon source, compound is carried out to the ball-milling treatment of 2.5h, carry out spraying dry afterwards;
(5) compound obtained after step (4) is sintered, the process regulation of sintering is: programming rate 2 DEG C/min, holding temperature 750 DEG C, temperature retention time 15 hours, naturally cool with stove, obtain physical and chemical performance and all excellent composite mixed and cladded type anode material for lithium-ion batteries LiFePO of electrical property
4.
Embodiment 3:
One is composite mixed and cladded type anode material for lithium-ion batteries LiFePO of the present invention as shown in Figure 3
4preparation method, comprise the following steps:
(1) raw material is purchased: purchase as the lithium hydroxide of raw material, ferrous oxalate, phosphoric acid and containing doped metallic elements compound, doping metals comprises Nb, Mg, Ti, Mn and Zn; Basic magnesium carbonate, titanium dioxide, manganese acetate, zinc acetate and niobium pentaoxide is referred to containing doped metallic elements compound; According to Li
0.984nb
0.01ti
0.006fe
0.98mg
0.01mn
0.006zn
0.004pO
4molecular formula prepare burden, consider the scaling loss in lithium source and phosphorus source in sintering process, mol ratio n (the Li)/n (Fe) of lithium source and source of iron is about 1.04, and mol ratio n (the P)/n (Fe) of phosphorus source and source of iron is about 1.03;
(2) mixing making beating: phosphorus source is placed in a container, adds containing doped metallic elements compound under the condition constantly stirred; Then continued mechanical stir, and lithium source is added wherein slip, adopt deionized water cooling slip, pour vertical mill into when slurry temperature drops to 45 DEG C, and add source of iron, continue Vertical Mill 2.5h; Collect slip; Carry out spraying dry, obtain powdery precursor;
(3) pre-burning: the powdery precursor that step (2) obtains is carried out pre-burning, and pre-burning system is: programming rate 3 DEG C/min, holding temperature 660 DEG C, temperature retention time 6.5 hours, cools naturally with stove;
(4) second batch: second batch and ball-milling treatment are carried out to the product after step (3) pre-burning, second batch allocates carbon source (selecting glucose as carbon source) in the product after pointing to pre-burning, the amount of allocating into of carbon source is by 5% of the product quality after pre-burning, after adding carbon source, compound is carried out to the ball-milling treatment of 1.5h, carry out spraying dry afterwards;
(5) compound obtained after step (4) is sintered, the process regulation of sintering is: programming rate 3 DEG C/min, holding temperature 770 DEG C, temperature retention time 18 hours, naturally cool with stove, obtain physical and chemical performance and all excellent composite mixed and cladded type anode material for lithium-ion batteries LiFePO of electrical property
4.
Embodiment 4:
One is composite mixed and cladded type anode material for lithium-ion batteries LiFePO of the present invention as shown in Figure 4
4preparation method, comprise the following steps:
(1) raw material is purchased: purchase as the lithium dihydrogen phosphate of raw material, ferrous oxalate and containing doped metallic elements compound, doping metals comprises Nb, Mg, Ti, Mn and Zn; Magnesium oxalate, titanium dioxide, manganese oxalate, zinc oxalate and niobium oxalate is referred to containing doped metallic elements compound; According to Li
0.95nb
0.01fe
0.967mg
0.016ti
0.004mn
0.005zn
0.004pO
4molecular formula prepare burden, consider the scaling loss in lithium source and phosphorus source in sintering process, mol ratio n (the Li)/n (Fe) of lithium source and source of iron is about 1.02, and mol ratio n (the P)/n (Fe) of phosphorus source and source of iron is about 1.04;
(2) mixing making beating: phosphorus source is placed in a container, adds containing doped metallic elements compound under the condition constantly stirred; Then continued mechanical stir, and lithium source is added wherein slip, adopt deionized water cooling slip, pour vertical mill into when slurry temperature drops to 50 DEG C, and add source of iron, continue Vertical Mill 2h; Collect slip; Carry out spraying dry, obtain powdery precursor;
(3) pre-burning: the powdery precursor that step (2) obtains is carried out pre-burning, and pre-burning system is: programming rate 4 DEG C/min, holding temperature 670 DEG C, temperature retention time 7 hours, cools naturally with stove;
(4) second batch: second batch and ball-milling treatment are carried out to the product after step (3) pre-burning, second batch allocates carbon source (selecting glucose as carbon source) in the product after pointing to pre-burning, the amount of allocating into of carbon source is by 5% of the product quality after pre-burning, after adding carbon source, compound is carried out to the ball-milling treatment of 2h, carry out spraying dry afterwards;
(5) compound obtained after step (4) is sintered, the process regulation of sintering is: programming rate 4 DEG C/min, holding temperature 780 DEG C, temperature retention time 15 hours, naturally cool with stove, obtain physical and chemical performance and all excellent composite mixed and cladded type anode material for lithium-ion batteries LiFePO of electrical property
4.
The granularity of the product that the above embodiment of the present invention 1 ~ 4 is obtained and specific surface as shown in table 1 below, electric performance test result is as shown in table 2 below.
Table 1: the granularity of the product that embodiment 1 ~ 4 is obtained and specific surface
Table 2: the electric performance test result of the product that embodiment 1 ~ 4 is obtained
Claims (9)
1. a composite mixed and cladded type anode material for lithium-ion batteries LiFePO
4preparation method, comprise the following steps:
(1) purchase as the lithium source of raw material, source of iron, phosphorus source and containing doped metallic elements compound, described doping metals comprises Nb, Mg, Ti, Mn and Zn; Mixing making beating, drying are carried out to raw material, obtains powdery precursor; Mol ratio n (the Li)/n (Fe)=0.98 ~ 1.06 of described lithium source and source of iron, mol ratio n (the P)/n (Fe)=0.98 ~ 1.05 of described phosphorus source and source of iron, the mol ratio in the total mole number of all doped metallic elements and phosphorus source, source of iron or lithium source is 0.001 ~ 0.05;
(2) powdery precursor that step (1) obtains is carried out pre-burning;
(3) second batch and ball-milling treatment are carried out to the product after step (2) pre-burning; Described second batch allocates carbon source in the product after pointing to pre-burning;
(4) compound obtained after step (3) is sintered, obtain anode material for lithium-ion batteries LiFePO
4.
2. preparation method according to claim 1, is characterized in that: lithium hydroxide, lithium dihydrogen phosphate or lithium carbonate are selected in described lithium source, and described source of iron selects ferrous oxalate, and phosphoric acid or lithium dihydrogen phosphate are selected in described phosphorus source; Ammonium salt is not adopted in described raw material.
3. preparation method according to claim 1, it is characterized in that: the described doping metals Mg element compound that contains comprises basic magnesium carbonate, magnesium acetate, magnesium hydroxide, one or more in magnesium oxalate, the described doping metals Ti element compound that contains comprises titanium dioxide, the described doping metals Mn element compound that contains comprises manganese acetate, basic carbonate manganese, one or more in manganese oxalate, the described doping metals Zn element compound that contains comprises zinc acetate, basic zinc carbonate, one or more in zinc oxalate, the described doping metals Nb element compound that contains comprises niobium pentaoxide and/or niobium oxalate.
4. preparation method according to claim 1, is characterized in that: the amount of allocating into of described carbon source is by 1% ~ 10% of pre-burning product quality.
5. preparation method according to claim 4, is characterized in that: described carbon source select in citric acid, sucrose, glucose, carbon black, soluble starch one or both.
6. preparation method according to claim 1, is characterized in that, the process regulation of pre-burning is in described step (2): programming rate 1 DEG C/min ~ 10 DEG C/min, holding temperature 400 DEG C ~ 700 DEG C, temperature retention time 1 ~ 20 hour, cools naturally with stove.
7. preparation method according to claim 1, is characterized in that, the process regulation of sintering is in described step (4): programming rate 1 DEG C/min ~ 10 DEG C/min, holding temperature 600 DEG C ~ 900 DEG C, temperature retention time 1 ~ 20 hour, cools naturally with stove.
8. preparation method according to claim 1, is characterized in that, the mixing pulping process in described step (1) refers to: described phosphorus source is placed in a container, adds containing doped metallic elements compound under the condition constantly stirred; Then continued mechanical stir, and lithium source is added wherein slip, adopt deionized water cooling slip, pour vertical mill into when slurry temperature drops to 30 DEG C ~ 60 DEG C, and add source of iron, continue Vertical Mill 0.5h ~ 4h; Collect slip; Adopt water as batch mixing medium during mixing.
9. the anode material for lithium-ion batteries LiFePO that preparation method obtains according to any one of claim 1 ~ 8
4, it is characterized in that: described anode material for lithium-ion batteries LiFePO
4middle mixing and doping has Nb, Mg, Ti, Mn and Zn five kinds of metallic elements, described anode material for lithium-ion batteries LiFePO
4d
501 μm ~ 2 μm, specific area is at 16m
2/ g ~ 21.5m
2/ g, tap density>=1.5g/cm
3.
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| CN103531794B (en) * | 2013-10-28 | 2015-12-02 | 金瑞新材料科技股份有限公司 | Lithium ferrous phosphate as anode material of lithium ion battery and preparation method thereof |
| CN103515601B (en) * | 2013-10-28 | 2016-03-02 | 金瑞新材料科技股份有限公司 | A kind of anode material for lithium ion battery LiFePO 4 and preparation method thereof |
| CN103972487B (en) * | 2014-05-16 | 2016-08-24 | 厦门钨业股份有限公司 | A kind of multicomponent composite oxide material and industrial production process thereof |
| FR3062384B1 (en) * | 2017-02-01 | 2021-02-12 | Centre Nat Rech Scient | PROCESS FOR THE PREPARATION OF A VANADIUM-CARBON PHOSPHATE COMPOSITE MATERIAL BY THE LIQUID ROUTE |
| GB201719637D0 (en) * | 2017-11-27 | 2018-01-10 | Johnson Matthey Plc | Cathode materials |
| CN108400330B (en) * | 2018-03-08 | 2020-07-14 | 蒋央芳 | Preparation method of carbon-doped manganese (III) phosphate |
| CN112340720B (en) * | 2019-08-06 | 2023-05-16 | 湖南师范大学 | Zinc ion battery positive electrode material based on doped zinc-manganese phosphate structure and synthesis method thereof |
| CN113148969B (en) * | 2021-04-08 | 2022-11-08 | 江苏力泰锂能科技有限公司 | Doped lithium iron manganese phosphate-carbon composite material and preparation method thereof |
| CN114613965A (en) * | 2022-03-22 | 2022-06-10 | 宜昌邦普循环科技有限公司 | Preparation method and application of lithium iron phosphate/carbon composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1195838A2 (en) * | 2000-10-06 | 2002-04-10 | Sony Corporation | Non-aqueous electrolyte cell |
| CN101638226A (en) * | 2009-08-28 | 2010-02-03 | 浙江贝能新材料科技有限公司 | Preparation method of spherical lithium iron phosphate |
| CN102751493A (en) * | 2012-06-27 | 2012-10-24 | 武陟县鑫凯科技材料有限公司 | Preparation method of lithium iron phosphate |
-
2013
- 2013-07-01 CN CN201310271596.4A patent/CN103346317B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1195838A2 (en) * | 2000-10-06 | 2002-04-10 | Sony Corporation | Non-aqueous electrolyte cell |
| CN101638226A (en) * | 2009-08-28 | 2010-02-03 | 浙江贝能新材料科技有限公司 | Preparation method of spherical lithium iron phosphate |
| CN102751493A (en) * | 2012-06-27 | 2012-10-24 | 武陟县鑫凯科技材料有限公司 | Preparation method of lithium iron phosphate |
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