CN101070149B - Lithium iron carbonate material prepared by vacuum carbon reduction and method - Google Patents
Lithium iron carbonate material prepared by vacuum carbon reduction and method Download PDFInfo
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- CN101070149B CN101070149B CN200710052395XA CN200710052395A CN101070149B CN 101070149 B CN101070149 B CN 101070149B CN 200710052395X A CN200710052395X A CN 200710052395XA CN 200710052395 A CN200710052395 A CN 200710052395A CN 101070149 B CN101070149 B CN 101070149B
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Abstract
This invention relates to a kind of anode material and method used for reducing preparation of lithium iron phosphate by vacuum carbon. It uses cheap phosphate, iron compound and lithium compound as raw material, compound of cheap heavy metal as adulteration modifying agent, cheap and abundant activated carbon, acetylene black and graphite as reducing agent. Dealing with it using ball milling techniques and makes solid-phase chemical reaction under the vacuum condition, then get the anode material adulterating lithium iron phosphate which contains carbon. Lithium iron phosphate compounded in this invention has a stable performance, physical chemistry of products has a good homogeneity and consistency and a high productivity; lithium iron phosphate produced in this invention has a high tapdensity and electric specific votume, good discharging capability of high-current, stable electrochemistry circulation capability, and low local action, besides, it is easy to control content of tantalum adulterated. The tap density of lithium iron phosphate produced by this method is 1.63-2.04g/cu cm, the highest discharging specific votume is 161.3mAh/g.
Description
Technical field
The present invention relates to the lithium ion battery material preparing technical field, specifically be meant lithium iron phosphate positive material of a kind of vacuum carbon reduction preparation and preparation method thereof.
Background technology
Lithium ion battery is the green high-capacity battery of a new generation, many good characteristics such as have that operating voltage height, energy density height, electrochemistry good cycle, self-discharge are little, memory-less effect, actual work temperature scope are wide.Therefore, since commercialization in 1992 was produced, lithium ion battery just was widely used in mobile telephone, removable computer, digital camera, digital camcorder, electronic instrument, military portable equipment etc.Enter 21 century, over particularly nearest 5 years, the fast development of lithium ion battery industry, the output of lithium ion battery also increases fast, and its Application Areas constantly enlarges, and has become this century to national economy and the significant new high-tech product of people's lives.Yet; up to the present; lithium ion battery is still based on lower volume, low battery power; the large-scale production of still being unrealized of heavy body, high-power lithium ion battery makes lithium ion battery not be used widely as yet at aspects such as large-capacity ups, big-and-middle-sized energy-storage battery, big-and-middle-sized power tool, electric bicycle car, electromobiles.Wherein one of major reason is exactly that anode active material of lithium ion battery does not make substantial breakthroughs as yet.
Positive electrode active materials is the important component part of lithium ion battery.Up to the present research the most in detail, positive electrode material is LiCoO the most widely
2, LiNiO
2, LiMn
2O
4And multicomponent composite oxide is (as LiNi
0.8Co
0.2O
2, LiNi
1/3Co
1/3Mn
1/3O
2) etc.LiCoO wherein
2It is the positive electrode material of unique realization large-scale industrial production.Present commodity lithium ion battery more than 90% also all is with LiCoO
2For positive electrode material is produced.Though LiCoO
2Have comparatively excellent electrochemical properties, but because very not abundant, the production technology cost height of its synthetic starting material, so its price is comparatively expensive.And LiCoO
2Have also that capacity lower (actual specific capacity has only about 120mAh/g), toxicity are big, poor safety performance etc. a series of problems.
Spinel type active material LiMn
2O
4Raw material and production cost is lower, safety performance is better, but its electrochemistry cycle performance, high temperature cyclic performance are poor, certain dissolving are arranged, by LiMn in electrolytic solution
2O
4The storge quality of the lithium ion battery of producing is poor, cycle life short.Novel poly-metal deoxide LiNi
1/3Co
1/3Mn
1/3O
2Material has been concentrated LiCoO
2, LiNiO
2, LiMn
2O
4Advantage separately Deng material: more or less freely synthetic, cost is relatively low, electrochemistry good cycle, reversible capacity are higher, Stability Analysis of Structures, safety performance are better, but owing to contain Co, the Ni of more costliness, material cost is also comparatively high.
Because the influence of above-mentioned these factors, though lithium ion battery has numerous premium propertiess, because the influence of factors such as price and safety performance, the research and the industrialization of power lithium-ion battery are walked with difficulty.And the production of heavy body, high-power lithium ion battery, the cost of its positive electrode material, high-temperature behavior, security are very important.LiCoO
2, LiNiO
2, LiMn
2O
4And the poly-metal deoxide positive electrode material can not satisfy the requirement of the production of large vol, high-power lithium ion battery fully.Therefore, research and development are applicable to that the novel anode material of large vol, superpower, good heavy current, lithium-ion-power cell that safety performance is high becomes the focus of correlative study.Olivine-type LiFePO
4Positive electrode material just in time possesses the desired advantage of the novel anode material that satisfies above-mentioned lithium-ion-power cell.
LiFePO
4Positive electrode material does not contain more valuable or yttrium, and raw material sources are very abundant; And LiFePO
4Stability Analysis of Structures, electrochemistry good cycle, theoretical specific capacity height (its theoretical capacity is 170mAh/g), sparking voltage moderate (3.2～3.4V), sparking voltage extremely steadily, the high (PO of safety performance
4 3-The difficult precipitated oxygen that decomposes takes place), high-temperature behavior, thermostability obviously are better than existing other all positive electrode materials.In addition, LiFePO
4Storge quality is good, nontoxic, pollution-free, is real environmental friendliness positive source material.With LiCoO
2, LiNiO
2, LiMn
2O
4And the derivative positive electrode material is compared LiFePO
4Positive electrode material is expected to become the positive electrode material of middle large vol, middle high power lithium ion cell first-selection having outstanding advantage aspect synthetic cost, chemical property, the security.LiFePO
4The industrialization of positive electrode material and popularization and application are to reducing the lithium ion battery cost, improve battery security, high-power lithium ion power cell industry when expansion lithium ion battery industry is special, promote that lithium ion battery maximizes, superpowerization has very significant meaning, the widespread use that makes lithium ion battery in middle large-capacity ups, medium-and-large-sized energy-storage battery, power tool, electromobile is become a reality.
At present, LiFePO
4The preparation method mainly contain solid reaction process, liquid phase process (coprecipitation method, hydrothermal method, sol-gel method and emulsion method etc.); the common feature of all existing methods is exactly the protection that needs mobile high purity inert gas or high pure nitrogen, and slumpability gas shield technology has increased the synthetic cost of iron lithium phosphate to a great extent.And, because all existing synthetic technologys are very imperfect, cause resulting iron lithium phosphate consistency of product relatively poor, that is to say the physics of different batches institute synthetic product, chemical homogeneity is poor, the chemical property quality is inconsistent, makes its production cost further improve.In addition, iron lithium phosphate also has self inherent shortcoming, mainly is that its tap density is lower, and its theoretical density is 3.6g/cm
3, its actual tap density generally has only 1.6-1.8g/cm
3And iron lithium phosphate is the relatively poor semiconductor material of conductivity.Immature and iron lithium phosphate self the inherent shortcoming of the existing synthetic technology of iron lithium phosphate, seriously hindered the large-scale industrial production process of iron lithium phosphate, also influence LiFePO 4 material at various types of lithium ion batteries, particularly lithium-ion-power cell is made the widespread use in field.
Summary of the invention
Purpose of the present invention is exactly in order to solve above-mentioned the deficiencies in the prior art, provides a kind of vacuum carbon reduction that is suitable for commercial scale production to prepare the method for lithium iron phosphate positive material.The technology used in the present invention synthesis technique flow process is simple, and the iron lithium phosphate product performance of production are stable, the product homogeneity is good, high conformity, productive rate height; Iron lithium phosphate tap density height, electric specific storage height, electrochemistry stable cycle performance, the self-discharge of the present invention's preparation is low, doped metallic elements content is easy to control.
The present invention is achieved through the following technical solutions: described a kind of vacuum carbon reduction prepares the method for lithium iron phosphate positive material, comprises the steps and processing condition:
The first step is 1: 1: 1 with Fe source compound, Li source compound and doping metals compound by the mol ratio of P: Fe: Li: M (M represents doping metals): the mixed of (0.001～0.05);
Second step placed vacuum high-energy ball milling jar with said mixture, was evacuated to 10
-2～10
-4Pa, ball milling 6～12 hours;
The 3rd step with carbonaceous reducing agent in Fe: the ratio of C mol ratio 1: 0.8～1.6, join in the good mixture of above-mentioned ball-milling processing, be evacuated to 10
-2～10
-4Pa continued ball milling 6～12 hours, obtained pre-reaction material;
The 4th step was transferred to above-mentioned reactant precursor in the vacuum reaction stove, fed high pure nitrogen 5～45 minutes, after be evacuated to 10
-2～10
-4Pa, heating, 450～850 ℃ of controlled temperature kept furnace temperature constant 8～24 hours, fed high pure nitrogen 5～45 minutes, and sealing is cooled to room temperature, obtains the metal-doped iron phosphate powder of carbon coated.
Iron lithium phosphate of the present invention forms by method for preparing.
In order to realize the present invention better, described Fe source compound comprises one or more in tertiary iron phosphate, ferrous phosphate, the ferric oxide; Described Li source compound comprises one or more in Lithium Oxide 98min, lithium hydroxide, the Trilithium phosphate; Described doping metals compound comprises one or more in aluminium dihydrogen phosphate, zinc oxide, magnesium oxide, the cobalt oxide; Described carbonaceous reducing agent comprises one or more in activated carbon, acetylene black, the graphite.
The present invention compared with prior art has following advantage and beneficial effect:
1, utilizes synthetic iron lithium phosphate of the present invention fully without the high-purity argon gas protection, use seldom and handle, greatly reduce the synthetic cost of iron lithium phosphate with high pure nitrogen;
2, utilizing the pre-reaction material of synthetic iron lithium phosphate of the present invention to carry out ball-milling processing, solid state reaction under vacuum condition also carries out under vacuum condition, thereby make reactant fully to contact to make that solid state reaction is carried out more thorough, improved the productive rate of iron lithium phosphate greatly;
3, utilize synthetic iron lithium phosphate of the present invention, because pre-reaction material is handled and fully activation at high-energy ball milling, make that the used temperature of reaction of synthesizing iron lithium phosphate is lower, the reaction times shortens, the also effectively lower energy consumption cost of synthetic technology, enhance productivity;
4, utilize synthetic iron lithium phosphate of the present invention, owing to contain doping metals and carbonaceous reducing agent in the pre-reaction material, and handle and thorough mixing, activation at high-energy ball milling, make a plurality of one steps of solid state reactions such as synthetic, the doping of iron lithium phosphate and carbon reduction finish, improved the combined coefficient of iron lithium phosphate greatly.
5, utilize synthetic iron lithium phosphate of the present invention, because containing the pre-reaction material of doped metal ion and carbonaceous reducing agent handles and fully activation at high-energy ball milling, make the synthetic solid state reaction of carbon reduction and the reaction solid state reaction of mixing carry out simultaneously, simplified the synthesis technique of iron lithium phosphate;
6, utilize synthetic iron lithium phosphate of the present invention, because the pre-reaction material that contains doped metal ion and carbonaceous reducing agent is handled and thorough mixing, activation at high-energy ball milling, make homogeneous that the solid state reaction of synthesizing iron lithium phosphate carries out, fully, make the resulting LiFePO 4 material of the technology of the present invention phase structure and chemical constitution homogeneous, do not contain the impurity phase of non-homogeneous;
7, utilize that synthetic iron lithium phosphate of the present invention crystallization is perfect, grain diameter is little, uniform particle diameter, tap density height, actual discharge specific storage height, electrochemistry cycle performance are good, starting material are than horn of plenty, cheapness; Grain diameter scope by the resulting iron lithium phosphate of the present invention is 1～3 μ m, and tap density is 1.63～2.04g/cm
3, high tap density surpasses prior art synthesizing iron lithium phosphate material tap density; The Experimental cell of being formed with resulting lithium iron phosphate anode active material of the present invention and metallic lithium, when being 3.4～4.2V, final discharging voltage 2.8V with 0.2C rate charge-discharge, charging voltage, the highest specific discharge capacity reaches 161.3mAh/g, is up to 91.2% through the capability retention after 33 charge and discharge cycles.
Description of drawings
Fig. 1 is the XRD diffracting spectrum of typical LiFePO 4 material;
Fig. 2 is the SEM figure of typical LiFePO 4 material;
Fig. 3 is that typical iron lithium phosphate is the discharge curve (Fig. 3 A) and the charge and discharge cycles specific discharge capacity figure (Fig. 3 B) of anodal experiment lithium cell.
Embodiment
Below in conjunction with drawings and Examples, the present invention is done detailed description further.
Embodiment one
The first step is 1: 1: 1 with tertiary iron phosphate and lithium hydroxide, aluminium dihydrogen phosphate by the mol ratio of P: Fe: Li: Al: 0.05 mixed;
Second step placed vacuum high-energy ball milling jar with said mixture, was evacuated to 10
-2Pa, ball milling 12 hours;
The 3rd step with the carbonaceous reducing agent activated carbon in Fe: 1: 0.8 ratio of C mol ratio, join in the good mixture of above-mentioned ball-milling processing, be evacuated to 10
-2Pa continued ball milling 6 hours, obtained pre-reaction material;
The 4th step was transferred to the vacuum reaction stove with above-mentioned reactant precursor, fed high pure nitrogen 5 minutes, after be evacuated to 10
-2Pa, heating, 450 ℃ of controlled temperature kept furnace temperature constant 24 hours, fed high pure nitrogen 45 minutes, and sealing is cooled to room temperature, obtains the metallic aluminium doped iron phosphate lithium powder of carbon coated.
Measure the particle diameter of above-mentioned iron lithium phosphate with particle-size analyzer, its particle diameter is 1～3 μ m, and median size is about 2 μ m, and its tap density is 1.76g/cm
3; Decided its crystalline structure with XRD (x-ray powder diffraction), the result shows that its crystalline structure is the olivine-type iron lithium phosphate; Its chemical property adopts with the iron lithium phosphate that to be that active substance is made anodal, be the LiPF of negative pole, 1M with the metal lithium sheet
6EC/DMC solution be that the Experimental cell of ionogen manufacturing is measured, the first discharge specific capacity that records its 0.2C multiplying power, final discharging voltage 2.8V discharge is 142.3mAh/g, the highest specific discharge capacity is 151.9mAh/g, capability retention is 90.1% after 50 charge and discharge cycles, has the favorable charge-discharge cycle performance.
Embodiment two
The first step with ferrous phosphate and Trilithium phosphate, doping metals compound aluminium dihydrogen phosphate, zinc oxide, magnesium oxide, (M represents doping metals, Al: Zn: Mg: the Co mol ratio is 1: 1: 1: mol ratio 0.5) is 1: 1: 1 to cobalt oxide: 0.03 mixed by P: Fe: Li: M;
Second step placed vacuum high-energy ball milling jar with said mixture, was evacuated to 10
-3Pa, ball milling 10 hours;
The 3rd step with carbonaceous reducing agent acetylene black, graphite (ratio is 1: 1) in Fe: 1: 1 ratio of C mol ratio, join in the above-mentioned mixture of handling well, be evacuated to 10
-3Pa continued ball milling 8 hours, obtained pre-reaction material;
The 4th step was transferred to the vacuum reaction stove with above-mentioned reactant precursor, fed high pure nitrogen 30 minutes, after be evacuated to 10
-3Pa, heating, 650 ℃ of controlled temperature kept furnace temperature constant 20 hours, fed high pure nitrogen 30 minutes, and sealing is cooled to room temperature, obtains the how metal-doped iron phosphate powder of carbon coated.
With XRD determining its crystalline structure of above-mentioned iron lithium phosphate, the result shows that its crystalline structure is olivine-type iron lithium phosphate (referring to accompanying drawing 1A); Measured its particle diameter with particle-size analyzer, and observed its outward appearance appearance with SEM, its its crystal habit subglobular, particle diameter is 1～3 μ m, synthetic median size is about 2 μ m (referring to accompanying drawing 2); Its tap density is 1.89g/cm
3, its chemical property adopts with the iron lithium phosphate that to be that active substance is made anodal, be the LiPF of negative pole, 1M with the metal lithium sheet
6EC/DMC solution be that the Experimental cell of ionogen manufacturing is measured, the first discharge specific capacity that records its 0.2C multiplying power, final discharging voltage 2.8V discharge is 139.6mAh/g, the highest specific discharge capacity is 161.3mAh/g, and capability retention is 91.2% (referring to accompanying drawing 3A, B) after 33 charge and discharge cycles.
Embodiment three
The first step with ferrous phosphate and Trilithium phosphate, zinc oxide by P: Fe: Li: the Zn mol ratio is 1: 1: 1: 0.02 mixed;
Second step placed vacuum high-energy ball milling jar with said mixture, was evacuated to 10
-2Pa, ball milling 11 hours;
The 3rd step with carbonaceous reducing agent graphite in Fe: 1: 1.4 ratio of C mol ratio, join in the good mixture of above-mentioned ball-milling processing, be evacuated to 10
-2Pa continued ball milling 9 hours, obtained pre-reaction material;
The 4th step was transferred to the vacuum reaction stove with above-mentioned reactant precursor, fed high pure nitrogen 5 minutes, after be evacuated to 10
-2Pa, heating, 550 ℃ of controlled temperature kept furnace temperature constant 20 hours, fed high pure nitrogen 45 minutes, and sealing is cooled to room temperature, obtains the metallic aluminium doped iron phosphate lithium powder of carbon coated.
Measure the particle diameter of above-mentioned iron lithium phosphate with particle-size analyzer, its particle diameter is 1～3 μ m, and median size is about 2 μ m; Its tap density is 1.63g/cm
3, having decided its crystalline structure with XRD (x-ray powder diffraction), the result shows that its crystalline structure is the olivine-type iron lithium phosphate; Its chemical property adopts with the iron lithium phosphate that to be that active substance is made anodal, be the LiPF of negative pole, 1M with the metal lithium sheet
6EC/DMC solution be that the Experimental cell of ionogen manufacturing is measured, the first discharge specific capacity that records its 0.2C multiplying power, final discharging voltage 2.8V discharge is 136.9mAh/g, the highest specific discharge capacity is 147.3mAh/g.
Embodiment four
The first step with tertiary iron phosphate and Lithium Oxide 98min, zinc oxide by P: Fe: Li: the Zn mol ratio is 1: 1: 1: 0.04 mixed;
Second step placed vacuum high-energy ball milling jar with said mixture, was evacuated to 10
-3Pa, ball milling 7 hours;
The 3rd step with carbonaceous reducing agent acetylene black in Fe: 1: 1.2 ratio of C mol ratio, join in the good mixture of above-mentioned ball-milling processing, be evacuated to 10
-3Pa continued ball milling 10 hours, obtained pre-reaction material;
The 4th step was transferred to the vacuum reaction stove with above-mentioned reactant precursor, fed high pure nitrogen 5 minutes, after be evacuated to 10
-2Pa, heating, 750 ℃ of controlled temperature kept furnace temperature constant 20 hours, fed high pure nitrogen 45 minutes, and sealing is cooled to room temperature, obtains the metallic aluminium doped iron phosphate lithium powder of carbon coated.
Measure the particle diameter of above-mentioned iron lithium phosphate with particle-size analyzer, its particle diameter is 1～3 μ m, and median size is about 1.5 μ m; Its tap density is 1.82g/cm
3, having decided its crystalline structure with XRD (x-ray powder diffraction), the result shows that its crystalline structure is the olivine-type iron lithium phosphate; Its chemical property adopts with the iron lithium phosphate that to be that active substance is made anodal, be the LiPF of negative pole, 1M with the metal lithium sheet
6EC/DMC solution be that the Experimental cell of ionogen manufacturing is measured, the first discharge specific capacity that records its 0.2C multiplying power, final discharging voltage 2.8V discharge is 131.3mAh/g, the highest specific discharge capacity is 152.2mAh/g.
Embodiment five
The first step with ferric oxide, Li source compound Trilithium phosphate and doping metals compound oxidation cobalt by P: Fe: Li: the Co mol ratio is 1: 1: 1: 0.001 mixed;
Second step placed vacuum high-energy ball milling jar with said mixture, was evacuated to 10
-4Pa, ball milling 11 hours;
The 3rd step is with carbonaceous reducing agent graphite, in Fe: 1: 1.6 ratio of C mol ratio, join in the above-mentioned mixture of handling well, and be evacuated to about 10
-4Pa continued ball milling 7 hours, obtained pre-reaction material;
The 4th step was transferred to the vacuum reaction stove with above-mentioned reactant precursor, fed high pure nitrogen 45 minutes, after be evacuated to 10
-4Pa, heating, 850 ℃ of controlled temperature kept furnace temperature constant 8 hours, fed high pure nitrogen 45 minutes, and sealing is cooled to room temperature, obtains the cobalt metal doped iron phosphate lithium powder of carbon coated.
Measure the particle diameter of above-mentioned iron lithium phosphate with particle-size analyzer, its particle diameter is 1～3 μ m, and median size is about 2 μ m; Its tap density is 2.04g/cm
3, having decided its crystalline structure with XRD, the result shows that its crystalline structure is olivine-type iron lithium phosphate (referring to accompanying drawing 1B); Its chemical property adopts with the iron lithium phosphate that to be that active substance is made anodal, be the LiPF of negative pole, 1M with the metal lithium sheet
6EC/DMC solution be that the Experimental cell of ionogen manufacturing is measured, the first discharge specific capacity that records its 0.1C, 0.2C and 0.5C multiplying power, final discharging voltage 2.8V discharge is respectively 159.6mAh/g, 151.0mAh/g and 136.5mAh/g.
As mentioned above, can realize the present invention preferably.
Claims (3)
1. a vacuum carbon reduction prepares the method for lithium iron phosphate positive material, it is characterized in that, comprises the steps:
The first step is 1: 1: 1 with Fe source compound, Li source compound and doping metals compound by the mol ratio of P: Fe: Li: M: the mixed of (0.001～0.05), and wherein M represents doping metals, described Fe source compound is tertiary iron phosphate or ferrous phosphate;
Second step mixed the mixture that obtains with the above-mentioned the first step and places vacuum high-energy ball milling jar, was evacuated to 10
-2～10
-4Pa, ball milling 6～12 hours;
The 3rd step with carbonaceous reducing agent by Fe: the ratio of C mol ratio 1: 0.8～1.6, join above-mentioned second and go on foot in the good mixture of ball-milling processing, be evacuated to 10
-2～10
-4Pa continued ball milling 6～12 hours, obtained pre-reaction material; Described carbonaceous reducing agent is one or more in activated carbon, acetylene black, the graphite;
The 4th step was transferred to above-mentioned reactant precursor in the vacuum reaction stove, fed high pure nitrogen 5～45 minutes, after be evacuated to 10
-2～10
-4Pa, heating, 350～850 ℃ of controlled temperature kept furnace temperature constant 8～24 hours, fed high pure nitrogen 5～45 minutes, and sealing is cooled to room temperature, obtains the metal-doped lithium iron phosphate positive material of carbon coated;
The described doping metals compound of the above-mentioned the first step comprises one or more in aluminium dihydrogen phosphate, zinc oxide, magnesium oxide, the cobalt oxide.
2. method according to claim 1 is characterized in that, the described Li source compound of the first step comprises one or more in Lithium Oxide 98min, lithium hydroxide, the Trilithium phosphate.
3. lithium iron phosphate positive material that is prepared from by the described method of claim 1.
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| KR101628416B1 (en) * | 2008-08-05 | 2016-06-08 | 다우 글로벌 테크놀로지스 엘엘씨 | Lithium metal phosphate/carbon nanocomposites as cathode active materials for rechargeable lithium batteries |
| CN102013490A (en) * | 2010-11-02 | 2011-04-13 | 三峡大学 | High rate lithium iron phosphate anode material and preparation method thereof |
| CN102227024B (en) * | 2011-05-23 | 2013-10-30 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium iron phosphate anode material for power lithium ion battery and preparation method thereof |
| CN102244245A (en) * | 2011-06-09 | 2011-11-16 | 上海大学 | Two-step carbothermic reduction preparation method of anode material LiFePO4/C of lithium ion battery |
| CN103500832B (en) * | 2013-10-23 | 2017-05-24 | 山东大学 | Method of preparing nanoscale lithium iron phosphate / carbon composite anode material |
| CN104332628B (en) * | 2014-09-04 | 2017-09-15 | 北汽福田汽车股份有限公司 | The preparation method and its lithium ion battery of anode material for lithium-ion batteries |
| JP6347268B2 (en) * | 2016-02-26 | 2018-06-27 | トヨタ自動車株式会社 | Method for producing composite active material |
| CN107994214B (en) * | 2017-11-14 | 2021-04-06 | 山东丰元化学股份有限公司 | High-performance lithium iron phosphate composite material and preparation method thereof |
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| CN1648036A (en) * | 2004-12-17 | 2005-08-03 | 清华大学 | Method for preparing Li Fe PO4 ball shape powder |
| CN1830764A (en) * | 2006-04-03 | 2006-09-13 | 清华大学 | Rare earth doped carbon clad type nanometer anode material iron lithium phosphate and its preparation method |
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| CN1648036A (en) * | 2004-12-17 | 2005-08-03 | 清华大学 | Method for preparing Li Fe PO4 ball shape powder |
| CN1830764A (en) * | 2006-04-03 | 2006-09-13 | 清华大学 | Rare earth doped carbon clad type nanometer anode material iron lithium phosphate and its preparation method |
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