CN102544508A - Preparation method of carbon-coated lithium iron phosphate composite material and iron phosphate anode - Google Patents
Preparation method of carbon-coated lithium iron phosphate composite material and iron phosphate anode Download PDFInfo
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- CN102544508A CN102544508A CN2011104456132A CN201110445613A CN102544508A CN 102544508 A CN102544508 A CN 102544508A CN 2011104456132 A CN2011104456132 A CN 2011104456132A CN 201110445613 A CN201110445613 A CN 201110445613A CN 102544508 A CN102544508 A CN 102544508A
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Abstract
The invention relates to a preparation method of a carbon-coated lithium iron phosphate composite material. The preparation method comprises the following steps: mixing ferric phosphate, lithium hydroxide and organic carbon source, ball-milling, spray drying, calcining, and crushing. The carbon-coated lithium iron phosphate composite material and a lithium iron phosphate battery anode prepared by the composite material have good electrical conductivity, tap density and electrochemical properties, are low in carbon content, suitable for industrial production and low in cost, and have good application prospects.
Description
Technical field
The present invention relates to the anode field, relate in particular to a kind of preparation method and iron phosphate lithium positive pole of composite ferric lithium phosphate material of carbon coating.
Background technology
Lithium ion battery is a kind of of electrochemical energy storage battery; Have energy density height, good cycle, memory-less effect, self-discharge rate is low and Environmental compatibility is good advantage; Obtain to develop rapidly in all kinds of consumer electronics sector, and demonstrate powerful potentiality in electric tool, electric automobile and electrification energy storage field.
The olivine-type LiFePO 4 has higher specific capacity as anode material for lithium-ion batteries, good cyclical stability, and fail safe reliably and cheap characteristics such as price become present academia and industrial circle Focal Point of Common Attention.This paper is purpose from the angle of practicality with carbon covering property and the chemical property that improves material, has discussed from solid phase synthesis and liquid phase production both direction and has optimized that carbon coats and to the influence of material electrochemical performance.
Because the lithium ion battery high energy density, it becomes battery with fastest developing speed on the market.On various portable electric appts such as mobile phone; Notebook computer, camera, widely apply in fields such as panel computer; And a lot of emerging fields are such as electric tool, and emergence such as electric bicycle etc. rapidly also make the production of lithium ion battery and use be the trend that increases sharply year by year.
Yet the development of lithium ion battery is faced with new challenges.Such as price factor, safety problem, energy density, fast charging and discharging ability, problems such as useful life hover on the body of lithium ion battery always, and particularly application motive-power battery and energy-storage battery are had higher requirement to lithium ion battery on the electric automobile.Develop the more electrode material of height ratio capacity and energy density, safe and reliable electrolyte is selected the suitable electrode material and the combination of electrolyte, and the power-supply management system of intelligent and safe all is heavy at present problem to be solved.
Comprise at a series of new compounds and to have polyanion (XO
4 2-, x=S, P, Si, As, Mo is in material w), with LiFePO
4Show the most outstandingly, it has satisfied the many key conditions as anode material of lithium battery: it can carry out reversible removal lithium embedded in a higher voltage (3.5v), has higher relatively weight ratio capacity 170mAhg
-1; Material can keep Stability Analysis of Structures overcharging and cross when putting, and is compatible with most electrolyte system.In addition, LiFePO
4There is environmental friendliness with triphylite at nature.Abundant raw material is cheap.
The research of relevant anode material for lithium-ion batteries has continued more than 20 year, and 10 years of particularly passing by are like a raging fire especially.Because early stage negative material concentrates on above the material with carbon element and does not have big breakthrough, so most of improvement about lithium ion battery all is around positive electrode.Yet in recent years, the introducing about nano composite material Sn/C/Co alloy and Si-C system made negative material that bigger progress arranged.Corresponding, seeking more, the positive electrode of high power capacity has become necessary to optimize battery system.
It is effectively to improve LiFePO that carbon coats
4The method of conductivity and chemical property.At LiFePO
4The preparation process in, carbon or carbonaceous organic material have a following effect: (1) is reduced to ferrous iron as reducing agent with ferric iron, perhaps suppresses ferrous oxidation; (2) stop being in contact with one another between the particle, particle grows up under the obstruction high temperature; (3) improve conductivity of electrolyte materials; (4) can reduce LiFePO
4Anodal dissolving in electrolyte.Yet it is the tap density that can reduce material that carbon coats the negative interaction that brings, and increases volume of battery, increases battery cost etc.So, the content of needs control carbon coated.In addition, carbon coats the otherwise negative effect that brings also needs further to analyze.
Seek the conductivity that a kind of method that can optimize the carbon coating improves carbon coated, can reduce carbon content simultaneously, can make LiFePO
4Tap density and chemical property between find a balance point.
Summary of the invention
The object of the invention is exactly preparation method and the iron phosphate lithium positive pole that a kind of composite ferric lithium phosphate material of carbon coating is provided in order to overcome the prior art deficiency.The present invention improves the conductivity of carbon coated through the method that can optimize carbon and coat, can reduce carbon content simultaneously, can make LiFePO
4Tap density and chemical property between find a balance point.
The object of the invention can realize through following technical scheme,
The present invention relates to a kind of preparation method of composite ferric lithium phosphate material of carbon coating, this method mainly may further comprise the steps: with ferric phosphate, lithium hydroxide and organic carbon source mixing, ball milling, spray drying, roasting, pulverizing.
The described organic carbon source of this method is glucose, polypropylene, soluble starch, Graphene or acetylene gas.
The described charging sequence of this method is ferric phosphate, organic carbon source, lithium hydroxide; Perhaps lithium hydroxide, organic carbon source, ferric phosphate.
The described ball milling method of this method is a wet method, is ball-milling medium with water.
Be catalyst with the ferrocene in the described process of this method.
It is anodal to the invention still further relates to a kind of ferric phosphate lithium cell, and the anode sizing agent that this anode adopts comprises composite ferric lithium phosphate material, conductive additive acetylene black and the binding agent PVDF that coats like aforesaid carbon.
Preferably, the adding proportion of composite ferric lithium phosphate material, conductive additive acetylene black and the binding agent PVDF of described carbon coating is 75～60: 15～30: 10.
Compared with prior art, the present invention has following beneficial effect: the present invention improves the conductivity of carbon coated through the method that can optimize carbon and coat, can reduce carbon content simultaneously, can make LiFePO
4Tap density and chemical property between find a balance point.
Description of drawings
Fig. 1 is the XRD figure of sample 1～4.
Fig. 2 is the SEM figure of sample 1～4.
Fig. 3 is the charging and discharging curve of sample 1～4.
Fig. 4 is the XRD figure of sample 5.
Fig. 5 is the XRD figure of sample 6 and sample 7.
Fig. 6 is the SEM figure of sample 6 and sample 7.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment provided detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Material characterizes
1, X-ray diffraction
This paper adopts powder polycrystalline X-ray diffraction method, and (X-ray diffraction XRD) carries out the crystal structure and the material phase analysis of material.Adopt the Rigaku D/Max-2550/PC type polycrystalline diffractometer of Japanese motor of science to carry out the material phase analysis of material.Use CuK during test
α(λ=1.54059
) be radiation source, pipe is pressed 40KV, pipe stream 250mA, scanning step is 0.02 °, sweep limits is 10 °～80 °.
2, the SEM of material microscopic appearance, tem observation
Adopt the S-4800 scanning electron microscopy (FESEM) of FDAC that material is observed, machine parameter is accelerating voltage 5kV during test.Take a morsel powdered sample in small-sized seed bottle, add the alcohol ultrasonic dispersing about 10 minutes.Suspension-turbid liquid after will disperseing with dropper drips on sample stage, dries naturally.And sample stage is carried out metal spraying handle.
Adopt NEC (JEOL) JEM-2010 (HR) type tem study the microstructure and the pattern of material.The powdered sample that takes a morsel is dispersed in the alcohol, through ultrasonic dispersing after 10 minutes, takes a morsel with capillary and to drip on copper mesh the infrared lamp oven dry.
(1) mixing of getting the raw materials ready: with the weighing respectively in proportion of ferric phosphate, glucose and lithium hydroxide, the adding in 1: 1 in molar ratio of ferric phosphate and lithium hydroxide, Fe: the C mol ratio is 1: 2;
(2) ball milling: in the polyurethane ball grinder, put into raw material, and add entry as ball-milling medium, the volume ratio of powder and medium is 1: 2, drum's speed of rotation 250rpm, ball milling 12 hours;
(3) spray drying: 220 ℃ of following spray dryings;
(4) roasting: 10 ℃/min be warmed up to 500 ℃ of insulations directly be warmed up to after 2 hours 700 ℃ continue insulation cooled off in 10 hours sample 1.
(5) sample that makes 1, acetylene black, PVDF are mixed with mass ratio at 75: 15: 10, are dispersed among an amount of NMP, continue to stir anode sizing agent, it is coated on the aluminium foil, 60 ℃ down the oven dry back flatten with press, make iron phosphate lithium positive pole.
Embodiment 2
(1) mixing of getting the raw materials ready: with ferric phosphate and lithium hydroxide 1: 1 in molar ratio respectively weighing add;
(2) ball milling: in the polyurethane ball grinder, put into raw material, and add entry as ball-milling medium, the volume ratio of powder and medium is 1: 2, drum's speed of rotation 250rpm, ball milling 12 hours; Fe: C=1 in molar ratio: 4 add polypropylene;
(3) spray drying: 220 ℃ of following spray dryings;
(4) roasting: 10 ℃/min be warmed up to 500 ℃ of insulations directly be warmed up to after 2 hours 700 ℃ continue insulation cooled off in 10 hours sample 2.
(5) sample that makes 2, acetylene black, PVDF are mixed with mass ratio at 60: 30: 10, are dispersed among an amount of NMP, continue to stir anode sizing agent, it is coated on the aluminium foil, 60 ℃ down the oven dry back flatten with press, make iron phosphate lithium positive pole.
Embodiment 3
(1) mixing of getting the raw materials ready: with the weighing respectively in proportion of ferric phosphate, glucose and lithium hydroxide, the adding in 1: 1 in molar ratio of ferric phosphate and lithium hydroxide, Fe: the C mol ratio is 1: 1;
(2) ball milling: in the polyurethane ball grinder, put into raw material, and add entry as ball-milling medium, the volume ratio of powder and medium is 1: 2, drum's speed of rotation 250rpm, ball milling 12 hours;
(3) spray drying: 260 ℃ of following spray dryings;
(4) roasting: 10 ℃/min be warmed up to 500 ℃ of insulations directly be warmed up to after 2 hours 700 ℃ continue insulation cooled off in 10 hours sample 3.
(5) sample that makes 3, acetylene black, PVDF are mixed with mass ratio at 70: 20: 10, are dispersed among an amount of NMP, continue to stir anode sizing agent, it is coated on the aluminium foil, 60 ℃ down the oven dry back flatten with press, make iron phosphate lithium positive pole.
Embodiment 4
(1) mixing of getting the raw materials ready: with the weighing respectively in proportion of ferric phosphate, soluble starch and lithium hydroxide, the adding in 1: 1 in molar ratio of ferric phosphate and lithium hydroxide, Fe: the C mol ratio is 1: 1;
(2) ball milling: in the polyurethane ball grinder, put into raw material, and add entry as ball-milling medium, the volume ratio of powder and medium is 1: 2, drum's speed of rotation 250rpm, ball milling 12 hours;
(3) spray drying: 260 ℃ of following spray dryings;
(4) roasting: 10 ℃/min be warmed up to 500 ℃ of insulations directly be warmed up to after 2 hours 700 ℃ continue insulation cooled off in 10 hours sample 4.
(5) sample that makes 4, acetylene black, PVDF are mixed with mass ratio at 75: 15: 10, are dispersed among an amount of NMP, continue to stir anode sizing agent, it is coated on the aluminium foil, 60 ℃ down the oven dry back flatten with press, make iron phosphate lithium positive pole.
Fig. 1 has provided the XRD figure spectrum of sample 1, sample 2, sample 3 and sample 4, as can be seen from the figure, and the XRD figure of these several samples spectrum and standard LiFePO
4It is fine that collection of illustrative plates meets ground, do not have the diffraction maximum of other dephasigns to occur.Make the finely dispersed powder of presoma.
Fig. 2 has provided the ESEM picture of sample 1, sample 2, sample 3 and sample 4.Can find out that it is spherical that powder is basically, these balls are reunited by a granule of hundreds of nanometer and are formed.Can analyze the carbon covered effect of different carbon sources from the pattern of these particles.Carry out the sample that carbon coats for adding polypropylene after the spray drying again; Carbon coats and can only carry out on the surface of spheric granules; And the surface of the primary particle that great majority are flocked together can not coat well; Will certainly reduce the conductivity of material monolithic, thereby influence the chemical property of material.Opposite; Use the carbon source of solubility before spray drying, to mix with powder; Can guarantee that powder primary particle and secondary agglomeration surface after the spray drying can both coat carbon equably, this fully improves conductivity of electrolyte materials and is undoubtedly favourable reducing the particle diameter of primary particle.On the other hand, organic carbon sources such as grape sugar and starch can increase the viscosity of precursor pulp to a certain extent, and form thicker carbon film on the aggregate surface easily, can hinder the diffusion of lithium ion to a certain extent.The pattern of comparative sample 1, sample 3 and sample 4 finds that the aggregate surface primary particle of sample 1 is not obvious, because of carbon source addition in its raw material many, so comparatively fine and close carbon film is arranged on the surface of aggregate.Sample 3 can be seen primary particle comparatively clearly on the aggregate surface with 4 in sample.Thus, we need add the solubility carbon source to obtain the LiFePO 4 that even carbon coats in presoma, and the content that need control carbon source again is too thick with reduction and the aggregate surface carbon film that prevents tap density.
What spray-dired inlet temperature influenced is the speed of slurry water evaporates and the water content of product.The drying of droplet is divided into two stages, the one, constant-rate drying period, the 2nd, falling rate drying period.Constant-rate drying period, the temperature of droplet keep wet-bulb temperature constant always, and surface moisture constantly evaporates, and the droplet internal moisture is to surface migration, and the water content of droplet constantly reduces, and dry air is constantly the heat transferred droplet, and the temperature of dry air reduces; Falling rate drying period droplet surface begins to solidify; Temperature Distribution raises to the outside from drop inside gradually, and it is high more that the moisture in the particle further reduces inlet temperature, and dry run gets into the falling rate drying period time just more early; Water evaporates is fast more, and the moisture content of product is low more.When inlet temperature was hanged down, the time of particle surface thousand dry curing was longer, and particle is reunited in striking process easily.The spheroid denser of sample 1 and sample 2, sample 3 is then loose relatively with sample 4, and this EAT spray-dired with it has very big relation.
The iron phosphate lithium positive pole that sample 1, sample 2, sample 3 and sample 4 are made is assembled into simulated battery respectively and carries out electrochemical property test; It is at 0.1C, and the charging and discharging curve under 0.5C and the 1C multiplying power is as shown in Figure 3.Comparative sample 1 can find that with sample 2 discharge capacity of sample 1 all is better than sample 2 under each multiplying power, and this has benefited from carbon coating more uniformly.Yet the overall performance of sample 1 and sample 2 is not high.This be because, when the spray drying temperature was low, precursor powder was long in the time of falling rate drying period, particle tends to solid, is unfavorable for taking off the embedding clang in the electrochemical reaction process.The charging and discharging curve of sample 3 and sample 4 then shows, improves the spray drying temperature and suitably reduces the chemical property that carbon content can significantly improve material.Improve the spray drying EAT atomizing particle moisture is issued additional rapidly,, help fully contacting of positive electrode and electrolyte, thereby improve chemical property at particle surface and the inner hole that forms.
Embodiment 5
(1) mixing of getting the raw materials ready: with the weighing respectively in proportion of ferric phosphate, glucose and lithium hydroxide, the adding in 1: 1 in molar ratio of ferric phosphate and lithium hydroxide, Fe: the C mol ratio is 1: 1, the order of adding is lithium hydroxide, ferric phosphate, glucose;
(2) ball milling: in the polyurethane ball grinder, put into raw material, and add entry as ball-milling medium, ball milling method is common stirring mill, ball milling 2 hours;
(3) spray drying: 220 ℃ of following spray dryings;
(4) roasting: 10 ℃/min be warmed up to 500 ℃ of insulations directly be warmed up to after 2 hours 700 ℃ continue insulation cooled off in 10 hours sample 5.
Embodiment 6
(1) mixing of getting the raw materials ready: with the weighing respectively in proportion of ferric phosphate, glucose and lithium hydroxide, the adding in 1: 1 in molar ratio of ferric phosphate and lithium hydroxide, Fe: the C mol ratio is 1: 1, the order of adding is ferric phosphate, glucose, lithium hydroxide;
(2) ball milling: in the polyurethane ball grinder, put into raw material, and add entry as ball-milling medium, ball milling method is common stirring mill, ball milling 3 hours;
(3) spray drying: 220 ℃ of following spray dryings;
(4) roasting: 10 ℃/min be warmed up to 500 ℃ of insulations directly be warmed up to after 2 hours 700 ℃ continue insulation cooled off in 10 hours sample 6.
Embodiment 7
(1) mixing of getting the raw materials ready: with the weighing respectively in proportion of ferric phosphate, glucose and lithium hydroxide, the adding in 1: 1 in molar ratio of ferric phosphate and lithium hydroxide, Fe: the C mol ratio is 1: 1, the order of adding is ferric phosphate, glucose, lithium hydroxide;
(2) ball milling: in the polyurethane ball grinder, put into raw material, and add entry as ball-milling medium, ball milling method stirs mill, ball milling 3 hours for circulation;
(3) spray drying: 300 ℃ of following spray dryings;
(4) roasting: 10 ℃/min be warmed up to 500 ℃ of insulations directly be warmed up to after 2 hours 700 ℃ continue insulation cooled off in 10 hours sample 7.
In the stirring-type ball milling, the interpolation of material order can influence degree of purity of production to a certain extent.As shown in Figure 4, the bright Fe that exists of the XRD figure stave of sample 5
2P
2O
7Phase and Li
3PO
4Phase.With FePO
4Join in the alkaline LiOH solution or above the powder, both meetings are reacted rapidly and generated Fe (OH)
3Red precipitate, and because Fe (OH)
3Reunion cause part material to be deposited on the bottom of ball grinder, the presoma in the ball grinder has departed from stoichiometric proportion to a certain extent, perhaps part has departed from the uniformity on the micro-scale, so dephasign can occur in the product.Certainly, this nonstoichiometry is than avoiding with the optimization ball-milling technology through changing charging sequence with microscopic uniformity.The charging sequence of sample 6 and sample 7 becomes evenly mixes FePO earlier in ball mill
4And C
6H
12O
6After slowly add LiOH, can avoid the vigorous reaction caking between each raw material, guarantee the uniformity of precursor pulp.Simultaneously, all can improve the ball milling effect through prolonging the ball milling time with introducing circulation ball milling.As shown in Figure 5, sample 6 and the XRD diffraction pattern of sample 7 and the LiFePO of standard
4It is fine that diffracting spectrum meets, and explains that the interpolation order through changing raw material can make the finely dispersed precursor pulp of micro-scale with the improvement ball-milling technology, and this also is the precondition that obtains pure phase product.
Need to prove that although the precursor pulp that can obtain to have good uniformity through ball milling, the solid constituent in the slurry is sedimentation easily in the process that leaves standstill.So before slurry gets into spray dryer, still need stir, prevent sedimentation.Therefore all slurries in this pilot scale process also need feeding while stirring to advance spray dryer after ball milling is intact.
Fig. 6 has provided the ESEM picture of sample 6 and sample 7.As can be seen from the figure, sample 6 is more prone to be agglomerated into bulky grain: when temperature was low, the time of particle entering falling rate drying period was long, and collision forms bulky grain each other easily.Can reduce the size of aggregate so improve the spray drying EAT, and obtain the uniform precursor powder of composition more easily.But meanwhile, improve the rising that spray-dired temperature means energy consumption.Therefore the speed that needs control charging rationally to be improving capacity usage ratio, guarantee evenly to be disperseed and particle size distribution even, under the prerequisite of the presoma that size is suitable, improve charging rate as far as possible.
Above content is to combine concrete preferred implementation to the further explain that the present invention did, and can not assert that specific embodiment of the present invention is confined to these explanations.For the those of ordinary skill of technical field according to the invention, make some substitute variants that are equal in following of the prerequisite that does not break away from the present invention's design and all should be regarded as belonging to protection scope of the present invention.
Claims (9)
1. the preparation method of the composite ferric lithium phosphate material of a carbon coating is characterized in that this method mainly may further comprise the steps: with ferric phosphate, lithium hydroxide and organic carbon source mixing, ball milling, spray drying, roasting, pulverizing; The mol ratio of said ferric phosphate and lithium hydroxide is 1: 1, Fe in said ferric phosphate and the organic carbon source: the C mol ratio is 1: 1.
2. the preparation method of the composite ferric lithium phosphate material that carbon as claimed in claim 1 coats is characterized in that described organic carbon source is glucose, polypropylene, soluble starch or Graphene.
3. the preparation method of the composite ferric lithium phosphate material that carbon as claimed in claim 1 coats is characterized in that described charging sequence is ferric phosphate, organic carbon source, lithium hydroxide.
4. the preparation method of the composite ferric lithium phosphate material that carbon as claimed in claim 1 coats is characterized in that described charging sequence is lithium hydroxide, organic carbon source, ferric phosphate.
5. the preparation method of the composite ferric lithium phosphate material that carbon as claimed in claim 1 coats is characterized in that described ball milling method is a wet method.
6. the preparation method of the composite ferric lithium phosphate material that carbon as claimed in claim 5 coats is characterized in that described mechanical milling process is medium with water.
7. the preparation method of the composite ferric lithium phosphate material that carbon as claimed in claim 1 coats is characterized in that, is catalyst with the ferrocene in the described process.
8. a ferric phosphate lithium cell positive pole is characterized in that, the anode sizing agent that this anode adopts comprises composite ferric lithium phosphate material, conductive additive acetylene black and the binding agent PVDF that carbon as claimed in claim 1 coats.
9. ferric phosphate lithium cell as claimed in claim 8 is anodal, it is characterized in that, the mass ratio of composite ferric lithium phosphate material, conductive additive acetylene black and binding agent PVDF that described carbon coats is 60～75: 15～30: 10.
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| CN104134801A (en) * | 2014-07-28 | 2014-11-05 | 北京万源工业有限公司 | Carbon nitride and graphene cladded lithium iron phosphate composite anode material and preparation method thereof |
| CN104134801B (en) * | 2014-07-28 | 2016-06-01 | 北京万源工业有限公司 | Carbonitride-graphene coated iron phosphate compound anode material of lithium and its preparation method |
| CN105529439A (en) * | 2014-10-27 | 2016-04-27 | 深圳市比克电池有限公司 | Method for preparing lithium iron phosphate by hydrothermal method and lithium iron phosphate prepared by method |
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| CN107845792A (en) * | 2017-10-20 | 2018-03-27 | 深圳市毓丰新材料有限公司 | A kind of LiFePO4 with loose structure/graphene composite lithium ion battery positive electrode |
| CN112331846A (en) * | 2019-08-27 | 2021-02-05 | 万向一二三股份公司 | Preparation method of high-rate positive electrode material lithium iron phosphate |
| CN113991117A (en) * | 2021-10-28 | 2022-01-28 | 骆驼集团资源循环襄阳有限公司 | Preparation method of lithium iron phosphate composite material |
| CN114744170A (en) * | 2022-04-02 | 2022-07-12 | 楚能新能源股份有限公司 | Preparation method of modified lithium iron phosphate cathode material and lithium ion battery |
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