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CN101070149A - 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 PDF

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CN101070149A
CN101070149A CNA200710052395XA CN200710052395A CN101070149A CN 101070149 A CN101070149 A CN 101070149A CN A200710052395X A CNA200710052395X A CN A200710052395XA CN 200710052395 A CN200710052395 A CN 200710052395A CN 101070149 A CN101070149 A CN 101070149A
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lithium
phosphate
lithium iron
vacuum
iron phosphate
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CN101070149B (en
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周环波
库宗军
周亚洲
龚春丽
丁瑜
葛杏莉
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Hubei Uee Energy Technology Co Ltd
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XIAOGAN COLLEGE
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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 tap density 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

A kind of LiFePO 4 material and method of vacuum carbon reduction preparation
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 (5)

1.一种真空碳还原制备磷酸铁锂正极材料的方法，其特征是，包括如下步骤：1. a method for preparing lithium iron phosphate cathode material by vacuum carbon reduction, is characterized in that, comprises the steps: 第一步将铁源化合物、锂源化合物及掺杂金属化合物按P∶Fe∶Li∶M的摩尔比为1∶1∶1∶(0.001～0.05)的比例混合，其中M表示掺杂金属；In the first step, the iron source compound, the lithium source compound and the doping metal compound are mixed in a molar ratio of P:Fe:Li:M of 1:1:1:(0.001-0.05), wherein M represents the doping metal; 第二步将上述第一步混合得到的混合物置于真空高能球磨罐中，抽真空至10-2～10-4Pa，球磨6～12小时；The second step is to place the mixture obtained in the above first step into a vacuum high-energy ball mill tank, vacuumize to 10 -2 ~ 10 -4 Pa, and ball mill for 6 to 12 hours; 第三步将碳还原剂按Fe∶C摩尔比1∶0.8～1.6的比例，加入到上述第二步球磨处理好的混合物中，抽真空至10-2～10-4Pa，继续球磨6～12小时，得到反应前驱物；In the third step, the carbon reducing agent is added to the mixture treated by ball milling in the second step above at the ratio of Fe:C molar ratio of 1:0.8 to 1.6, and the vacuum is evacuated to 10 -2 ~ 10 -4 Pa, and the ball milling is continued for 6 ~ 12 hours, obtain reaction precursor; 第四步将上述反应物前驱物转移至真空反应炉中，通入高纯氮气5～45分钟，后抽真空至10-2～10-4Pa，加热，控制温度350～850℃，保持炉温恒定8～24小时，通入高纯氮气5～45分钟，密封冷却至室温，得到包覆碳的金属掺杂磷酸铁锂正极材料。The fourth step is to transfer the above-mentioned reactant precursor to a vacuum reaction furnace, pass high-purity nitrogen gas for 5 to 45 minutes, then evacuate to 10 -2 to 10 -4 Pa, heat, control the temperature at 350 to 850°C, and keep the furnace The temperature is kept constant for 8-24 hours, high-purity nitrogen gas is introduced for 5-45 minutes, sealed and cooled to room temperature, and a carbon-coated metal-doped lithium iron phosphate positive electrode material is obtained. 2.根据权利要求权利要求1所述的方法，其特征是，第一步所述铁源化合物包括磷酸铁、磷酸亚铁、三氧化二铁中的一种或几种。2. The method according to claim 1, wherein the iron source compound in the first step comprises one or more of ferric phosphate, ferrous phosphate, and ferric oxide. 3.根据权利要求1或2所述的方法，其特征是，第一步所述的锂源化合物包括氧化锂、氢氧化锂、磷酸锂中的一种或几种。3. The method according to claim 1 or 2, wherein the lithium source compound in the first step comprises one or more of lithium oxide, lithium hydroxide, and lithium phosphate. 4.根据权利要求1或2所述的方法，其特征是，第一步所述的掺杂金属化合物包括磷酸二氢铝、氧化锌、氧化镁、氧化钴中的一种或几种。4. The method according to claim 1 or 2, characterized in that the doping metal compound in the first step comprises one or more of aluminum dihydrogen phosphate, zinc oxide, magnesium oxide, and cobalt oxide. 5.一种通过权利要求1所述方法制备而成的真空碳还原制备的磷酸铁锂正极材料。5. A lithium iron phosphate cathode material prepared by vacuum carbon reduction prepared by the method according to claim 1.
CN200710052395XA 2007-06-07 2007-06-07 Lithium iron carbonate material prepared by vacuum carbon reduction and method Expired - Fee Related CN101070149B (en)

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CN102013490A (en) * 2010-11-02 2011-04-13 三峡大学 High rate lithium iron phosphate anode material and preparation method thereof
CN102137811A (en) * 2008-08-05 2011-07-27 陶氏环球技术有限责任公司 Lithium metal phosphate/carbon nanocomposites as cathode active materials for rechargeable lithium batteries
CN102227024A (en) * 2011-05-23 2011-10-26 深圳市贝特瑞新能源材料股份有限公司 Positive electrode material lithium iron phosphate suitable for power lithium ion battery and preparation method thereof
CN102244245A (en) * 2011-06-09 2011-11-16 上海大学 Two-step carbothermal reduction preparation method of lithium-ion battery cathode material LiFePO4/C
CN103500832A (en) * 2013-10-23 2014-01-08 山东大学 Method of preparing nanoscale lithium iron phosphate / carbon composite anode material
CN104332628A (en) * 2014-09-04 2015-02-04 北汽福田汽车股份有限公司 Preparation method and lithium ion battery of lithium ion battery positive material
CN107134588A (en) * 2016-02-26 2017-09-05 丰田自动车株式会社 The manufacture method of active material
CN107994214A (en) * 2017-11-14 2018-05-04 山东丰元化学股份有限公司 A kind of high-performance iron phosphate lithium composite material and preparation method thereof

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