CN102208624A - Method for preparing carbon-coated LiFePO4 anode material by using low-temperature solid-phase method - Google Patents
Method for preparing carbon-coated LiFePO4 anode material by using low-temperature solid-phase method Download PDFInfo
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Abstract
The invention discloses a method for preparing a carbon-coated LiFePO4 anode material by using a low-temperature solid-phase method, comprising the following steps: 1, weighing iron phosphate and a lithium source based on the mole ratio of ferrum to lithium being 1: (1-1.05); weighing fatty acids in accordance with a ratio that 7.5-30g of fatty acids are added in per mole of iron phosphate; dissolving the weighed fatty acids in an organic solvent; and adding the weighed iron phosphate and the lithium source to the organic solvent of the fatty acids and then sufficiently mixing and grinding to obtain a precursor; and 2, carrying out calcination on the precursor obtained in the step 1 for 0.5-12 hours at a temperature of 400-700 DEG C under a non-oxide atmosphere and cooling to obtain the carbon-coated LiFePO4 anode material. The method is simple in operation without special equipment, and energy-saving and efficient due to carrying out the calcination once only. The method is used to obtain the carbon-coated LiFePO4 with even particle size distribution and good cyclical stability, which can be used as the anode material of a lithium ion secondary battery.
Description
Technical field
The invention belongs to technical field of lithium ion secondary, relate in particular to a kind of method for preparing the carbon cladded ferrous lithium phosphate positive electrode.
Background technology
Lithium rechargeable battery has been subjected to people's extensive concern with its good cycle, voltage and energy density advantages of higher.Wherein, positive electrode is the emphasis of research as influencing one of key of battery performance always.Cobalt acid lithium, lithium nickelate, LiMn2O4 and the multiple element compound are present four kinds of main positive electrodes.Along with the continuous expansion in lithium ion battery applications field, positive electrode need have good cycle performance, high specific capacity, stable chemical property, cheap characteristics such as cost.Because cobalt belongs to scarce resource and poisonous, lithium nickelate and the multiple element compound preparation difficulty, LiMn2O4 high-temperature behavior and cycle performance are poor, thereby above-mentioned material can't meet the demands.And has the LiFePO 4 (LiFePO of olivine structural
4) because of its good cycle, specific capacity height, stable electrochemical property, cheap, but after Goodenough seminar in 1997 finds its performance with removal lithium embedded, become a kind of lithium ion secondary battery anode material that is widely studied.The theoretical specific capacity of LiFePO 4 is 170 mAh/g, discharge platform is 3.4 V, though its discharge platform is a little less than cobalt acid lithium, but discharge steadily, the potential safety hazard that overcharges or put excessively is low, therefore at lithium ion battery, particularly required electrical source of power aspect such as electric motor car, electric tool has broad application prospects.
LiFePO 4 exists conductivity and the low shortcoming of ions diffusion speed, and for overcoming this shortcoming, people take several different methods, and are as coated with conductive oxide, conducting polymer, conductive carbon etc., wherein maximum with the research of carbon cladded ferrous lithium phosphate.At present, the synthetic method of carbon cladded ferrous lithium phosphate mainly contains hydrothermal carbonization method, carbothermic method, organic carbon source pyrolysis carbonizatin method etc.The hydrothermal carbonization method need be reacted in the water heating kettle of high temperature high voltage resistant, is unfavorable for continuous production; Carbothermic method need be 700
oCarry out under above high temperature of C and the non-oxidizing atmosphere, and product reunites easily, easily produce the impurity phase, product quality is difficult to control; The method of organic carbon source pyrolysis carbonization is with organic carbon source, as glucose, sucrose, polymer, mix with lithium source, source of iron and phosphorus source, pyrolysis carbonization under non-oxidizing atmosphere then, obtain carbon cladded ferrous lithium phosphate, but because organic carbon source thermal stability difference, the temperature of pyrolysis carbonization is also different, generally all needs 600
oThe high temperature that C is above, and need repeatedly calcine and grind, during consumption energy consumption.
Summary of the invention
At the deficiency that prior art exists, the present invention proposes a kind of special installation, simple to operate, method that low-temperature solid-phase method efficient energy-saving prepares the carbon cladded ferrous lithium phosphate positive electrode of need not.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of low-temperature solid-phase method prepares the method that the carbon newspaper covers lithium iron phosphate cathode material, may further comprise the steps:
1) mol ratio by iron and lithium is 1:(1 ~ 1.05) take by weighing ferric phosphate and lithium source, take by weighing aliphatic acid by every mole of phosphoric acid iron consumption 7.5 ~ 30g aliphatic acid again, the aliphatic acid that takes by weighing is dissolved in organic solvent, and ferric phosphate that adding takes by weighing in the organic solution of aliphatic acid and lithium source are after abundant mixed grinding obtains presoma;
2) with the presoma of step 1) gained in non-oxidizing atmosphere, in 400 ~ 700
oC is calcining 0.5 ~ 12h down, promptly obtains the carbon cladded ferrous lithium phosphate positive electrode after the cooling.
As preferably:
1) before calcining, described presoma stirred in air and make its natural evaporation to the mass percent of organic solvent wherein be not more than 60%;
2) be nanoscale as raw-material ferric phosphate and lithium source;
3) the lithium source is single thing or the composition more than two in lithium hydroxide, lithium carbonate, the lithium acetate;
4) aliphatic acid is single thing or the composition more than two in stearic acid, oleic acid, laurate, the palmitic acid;
5) non-oxidizing atmosphere is single thing or its both composition in nitrogen, argon gas, the helium;
6) organic solvent is alcohol or acetone.
Compared with prior art, the inventive method has the following advantages and beneficial effect:
1, the inventive method need not special installation, and is simple to operate, is suitable for industrialization and generates;
2, the inventive method only needs once calcining, efficient energy-saving;
3, adopt the inventive method 400 ~ 700
oThe low temperature of C can obtain the carbon cladded ferrous lithium phosphate that particle size distribution is even, cyclical stability is excellent down, its carbon content (mass percentage content) is 2 ~ 10%, the charging and discharging capacity of following 50 circulations of 1C multiplying power can be stabilized in 140 ~ 158 mAh/g, batch high conformity.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 1;
Fig. 2 is high resolution transmission electron microscopy (HRTEM) figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 1;
Fig. 3 is ESEM (SEM) figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 1;
Fig. 4 is the charging and discharging curve figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 1;
Fig. 5 is X-ray diffraction (XRD) collection of illustrative plates of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 2;
Fig. 6 is high resolution transmission electron microscopy (HRTEM) figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 2;
Fig. 7 is the charging and discharging curve figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 2;
Fig. 8 is carbon cladded ferrous lithium phosphate 200 times circulate under the 1C multiplying power charging and discharging capacity and the efficient that embodiment 2 is synthesized;
Fig. 9 is the charging and discharging curve figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 3;
Figure 10 is the charging and discharging curve figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 4;
Figure 11 is the charging and discharging curve figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 5;
Figure 12 is the charging and discharging curve figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 6;
Figure 13 is the charging and discharging curve figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 7;
Figure 14 is the charging and discharging curve figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 8;
Figure 15 is the charging and discharging curve figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 9;
Figure 16 is X-ray diffraction (XRD) collection of illustrative plates of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 10;
Figure 17 is high resolution transmission electron microscopy (HRTEM) figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 10;
Figure 18 is the charging and discharging curve figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 10;
Figure 19 is the charging and discharging curve figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 11;
Figure 20 is the charging and discharging curve figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 12;
Figure 21 is the charging and discharging curve figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 13;
Figure 22 is the charging and discharging curve figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 14;
Figure 23 is the charging and discharging curve figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 15;
Figure 24 is the charging and discharging curve figure of the carbon cladded ferrous lithium phosphate that synthesized of embodiment 16.
Embodiment
After the inventive method takes by weighing ferric phosphate, lithium source and carbon source in proportion, the raw material mixed grinding that takes by weighing fully is warmed up to 400～700 in the back in non-oxidizing atmosphere
oC also calcines 0.5～12h, promptly obtains carbon cladded ferrous lithium phosphate, and wherein, the mol ratio of iron and lithium is 1:(1 ~ 1.05 in ferric phosphate and the lithium source).In raw-material mixed process, fatty acid molecule and lithium source react and generate the fatty acid lithium mineralization in ferric phosphate and lithium source solid particles surface and space; Utilize the catalytic dehydrogenation of ferric phosphate, can reduce the carbon temperature.The aliphatic acid lithium salts that generates decomposes carbonization at low temperatures and simultaneously ferric iron is reduced to ferrous iron.Afterwards, reaction system generates LiFePO 4 without middle phase direct crystallization, simultaneously carbon is coated on grain surface equably, realize original position bag carbon, change the appearance that not exclusively causes the impurity phase in the middle of can preventing so mutually, can also reduce calcining heat, simultaneously generated in-situ carbon suppresses the growth of crystal grain, is beneficial to the distribution of sizes of control crystal grain.
The concrete steps of the inventive method are as follows:
1) mol ratio by iron and lithium is 1:(1 ~ 1.05) take by weighing ferric phosphate and lithium source, take by weighing aliphatic acid by every mole of phosphoric acid iron consumption 7.5 ~ 30g aliphatic acid again, the aliphatic acid that takes by weighing is dissolved in organic solvent, and ferric phosphate that adding takes by weighing in the organic solution of aliphatic acid and lithium source are after abundant mixed grinding obtains presoma; Above-mentioned mixed grinding adopts industrial mixed grinding equipment commonly used such as ball milling, colloid mill, sand milling; As preferably, above-mentionedly be nanoscale as raw-material ferric phosphate and lithium source; Above-mentioned lithium source is single thing or the composition more than two in lithium hydroxide, lithium carbonate, the lithium acetate; Above-mentioned aliphatic acid is single thing or the composition more than two in stearic acid, oleic acid, laurate, the palmitic acid; Above-mentioned organic solvent can be alcohol or acetone;
2) with the presoma of step 1) gained in non-oxidizing atmosphere, in 400 ~ 700
oC is calcining 0.5 ~ 12h down, promptly obtains the carbon cladded ferrous lithium phosphate positive electrode after the cooling; As preferably, presoma is carried out following processing before calcining: stirring presoma in air, to make its natural evaporation to the mass percent of organic solvent wherein be 10 ~ 60%; Above-mentioned non-oxidizing atmosphere is single thing or its both composition in nitrogen, argon gas, the helium.
For a better understanding of the present invention, the present invention will be further described below in conjunction with embodiment.
Embodiment 1
Mol ratio by iron and lithium is 1:1 weighing ferric phosphate and lithium hydroxide, takes by weighing stearic acid in the stearic ratio of every mole of phosphoric acid iron consumption 20g, and the stearic acid that takes by weighing is dissolved in the absolute ethyl alcohol, and being mixed with concentration is the stearic ethanolic solution of 10 g/L.Ferric phosphate, lithium hydroxide and stearic ethanolic solution are mixed back ball milling 8 hours in high energy ball mill, the pulpous state presoma that obtains behind the ball milling is stirred in air to make the mass percent of its natural evaporation absolute ethyl alcohol extremely wherein be 50%.Presoma after natural evaporation is put into porcelain boat, push tube furnace, under argon gas atmosphere, 400
oC calcined 3 hours down, took out the gained solid with stove cooling back, through the levigate black powder shape product carbon cladded ferrous lithium phosphate that promptly obtains.
The mass percentage content of carbon is 5% in the present embodiment products therefrom, particle diameter 40～160 nm, and the charging and discharging capacity of following 50 circulations of 1C multiplying power is 153 mAh/g.Figure 1 shows that powder crystal diffraction (XRD) collection of illustrative plates of present embodiment products therefrom, Figure 2 shows that high resolution transmission electron microscopy (HRTEM) figure of present embodiment products therefrom, Fig. 3 is ESEM (SEM) figure of present embodiment products therefrom, and Fig. 4 is the charging and discharging curve of present embodiment products therefrom under the 1C multiplying power.
Mol ratio by iron and lithium is 1:1 weighing ferric phosphate and lithium hydroxide, takes by weighing stearic acid in the stearic ratio of every mole of phosphoric acid iron consumption 20g, and the stearic acid that takes by weighing is dissolved in the absolute ethyl alcohol, and being mixed with concentration is the stearic ethanolic solution of 10 g/L.Ferric phosphate, lithium hydroxide and stearic ethanolic solution are mixed back ball milling 8 hours in high energy ball mill, the pulpous state presoma that obtains behind the ball milling is stirred in air to make the mass percent of its natural evaporation absolute ethyl alcohol extremely wherein be 60%.Presoma after natural evaporation is put into porcelain boat, push tube furnace, under argon gas atmosphere, 400
oC calcined 6 hours down, took out the gained solid with stove cooling back, through the levigate black powder shape product carbon cladded ferrous lithium phosphate that promptly obtains.
The mass percentage content of carbon is 7% in the present embodiment products therefrom, particle diameter 60～180 nm, and the charging and discharging capacity of following 200 circulations of 1C multiplying power is 159 mAh/g, the charging and discharging capacity of following 50 circulations of 5C multiplying power can reach 125 mAh/g.Fig. 5 is the XRD figure spectrum of present embodiment products therefrom, Fig. 6 is the HRTEM figure of present embodiment products therefrom, Fig. 7 is the charging and discharging curve of present embodiment products therefrom under the 1C multiplying power, Fig. 8 is the charging and discharging capacity and the efficient of present embodiment products therefrom 200 circulations under the 1C multiplying power, as seen from Figure 8, the present embodiment products therefrom has excellent cyclical stability.
Embodiment 3
Mol ratio by iron and lithium is 1:1 weighing ferric phosphate and lithium hydroxide, takes by weighing stearic acid in the stearic ratio of every mole of phosphoric acid iron consumption 20g, and the stearic acid that takes by weighing is dissolved in the absolute ethyl alcohol, and being mixed with concentration is the stearic ethanolic solution of 10 g/L.Ferric phosphate, lithium hydroxide and stearic ethanolic solution are mixed back ball milling 8 hours in high energy ball mill, the pulpous state presoma that obtains behind the ball milling is stirred in air to make the mass percent of its natural evaporation absolute ethyl alcohol extremely wherein be 0%.Presoma after natural evaporation is put into porcelain boat, push tube furnace, under argon gas atmosphere, 400
oC calcined 0.5 hour down, took out the gained solid with stove cooling back, through the levigate black powder shape product carbon cladded ferrous lithium phosphate that promptly obtains.
The mass percentage content of carbon is 8% in the present embodiment products therefrom, particle diameter 40～120 nm, and the charging and discharging capacity of following 50 circulations of 1C multiplying power is 145 mAh/g (as shown in Figure 9).
Embodiment 4
Mol ratio by iron and lithium is 1:1 weighing ferric phosphate and lithium hydroxide, takes by weighing stearic acid in the stearic ratio of every mole of phosphoric acid iron consumption 20g, and the stearic acid that takes by weighing is dissolved in the absolute ethyl alcohol, and being mixed with concentration is the stearic ethanolic solution of 10 g/L.Ferric phosphate, lithium hydroxide and stearic ethanolic solution are mixed back ball milling 8 hours in high energy ball mill, the pulpous state presoma that obtains behind the ball milling is stirred in air to make the mass percent of its natural evaporation absolute ethyl alcohol extremely wherein be 50%.Presoma after natural evaporation is put into porcelain boat, push tube furnace, under argon gas atmosphere, 400
oC calcined 12 hours down, took out the gained solid with stove cooling back, through the levigate black powder shape product carbon cladded ferrous lithium phosphate that promptly obtains.
The mass percentage content of carbon is 8% in the present embodiment products therefrom, particle diameter 80～180 nm, and the charging and discharging capacity of following 50 circulations of 1C multiplying power is 144mAh/g (as shown in figure 10).
Embodiment 5
Mol ratio by iron and lithium is 1:1 weighing ferric phosphate and lithium hydroxide, takes by weighing stearic acid in the stearic ratio of every mole of phosphoric acid iron consumption 20g, and the stearic acid that takes by weighing is dissolved in the absolute ethyl alcohol, and being mixed with concentration is the stearic ethanolic solution of 10 g/L.Ferric phosphate, lithium hydroxide and stearic ethanolic solution are mixed back ball milling 8 hours in high energy ball mill, the pulpous state presoma that obtains behind the ball milling is stirred in air to make the mass percent of its natural evaporation absolute ethyl alcohol extremely wherein be 50%.Presoma after natural evaporation is put into porcelain boat, push tube furnace, under argon gas atmosphere, 500
oC calcined 6 hours down, took out the gained solid with stove cooling back, through the levigate black powder shape product carbon cladded ferrous lithium phosphate that promptly obtains.
The mass percentage content of carbon is 6% in the present embodiment products therefrom, particle diameter 60～180 nm, and the charging and discharging capacity of following 50 circulations of 1C multiplying power is 154 mAh/g (as shown in figure 11).
Embodiment 6
Mol ratio by iron and lithium is 1:1 weighing ferric phosphate and lithium hydroxide, takes by weighing stearic acid in the stearic ratio of every mole of phosphoric acid iron consumption 20g, and the stearic acid that takes by weighing is dissolved in the absolute ethyl alcohol, and being mixed with concentration is the stearic ethanolic solution of 10 g/L.Ferric phosphate, lithium hydroxide and stearic ethanolic solution are mixed back ball milling 8 hours in high energy ball mill, the pulpous state presoma that obtains behind the ball milling is stirred in air to make the mass percent of its natural evaporation absolute ethyl alcohol extremely wherein be 50%.Presoma after natural evaporation is put into porcelain boat, push tube furnace, under argon gas atmosphere, 700
oC calcined 6 hours down, took out the gained solid with stove cooling back, through the levigate black powder shape product carbon cladded ferrous lithium phosphate that promptly obtains.
The mass percentage content of carbon is 3% in the present embodiment products therefrom, particle diameter 80～200 nm, and the charging and discharging capacity of following 50 circulations of 1C multiplying power is 150 mAh/g (as shown in figure 12).
Embodiment 7
Mol ratio by iron and lithium is 1:1 weighing ferric phosphate and lithium hydroxide, takes by weighing stearic acid in the stearic ratio of every mole of phosphoric acid iron consumption 7.5g, and the stearic acid that takes by weighing is dissolved in the absolute ethyl alcohol, and being mixed with concentration is the stearic ethanolic solution of 10 g/L.Ferric phosphate, lithium hydroxide and stearic ethanolic solution are mixed back ball milling 8 hours in high energy ball mill, the pulpous state presoma that obtains behind the ball milling is stirred in air to make its natural evaporation absolute ethyl alcohol mass percent extremely wherein be 50%.Presoma after natural evaporation is put into porcelain boat, push tube furnace, under argon gas atmosphere, 400
oC calcined 6 hours down, took out the gained solid with stove cooling back, through the levigate black powder shape product carbon cladded ferrous lithium phosphate that promptly obtains.
The mass percentage content of carbon is 2% in the present embodiment products therefrom, particle diameter 80～180 nm, and the charging and discharging capacity of following 50 circulations of 1C multiplying power is 140 mAh/g (as shown in figure 13).
Embodiment 8
Mol ratio by iron and lithium is 1:1 weighing ferric phosphate and lithium hydroxide, takes by weighing stearic acid in the stearic ratio of every mole of phosphoric acid iron consumption 15g, and the stearic acid that takes by weighing is dissolved in the absolute ethyl alcohol, and being mixed with concentration is the stearic ethanolic solution of 10 g/L.Ferric phosphate, lithium hydroxide and stearic ethanolic solution are mixed back ball milling 8 hours in high energy ball mill, the pulpous state presoma that obtains behind the ball milling is stirred in air to make its natural evaporation absolute ethyl alcohol mass percent extremely wherein be 50%.Presoma after natural evaporation is put into porcelain boat, push tube furnace, under argon gas atmosphere, 400
oC calcined 3 hours down, took out the gained solid with stove cooling back, through the levigate black powder shape product carbon cladded ferrous lithium phosphate that promptly obtains.
The mass percentage content of carbon is 4% in the present embodiment products therefrom, particle diameter 60～180 nm, and the charging and discharging capacity of following 50 circulations of 1C multiplying power is 146 mAh/g (as shown in figure 14).
Embodiment 9
Mol ratio by iron and lithium is 1:1 weighing ferric phosphate and lithium hydroxide, takes by weighing stearic acid in the stearic ratio of every mole of phosphoric acid iron consumption 30g, and the stearic acid that takes by weighing is dissolved in the absolute ethyl alcohol, and being mixed with concentration is the stearic ethanolic solution of 10 g/L.Ferric phosphate, lithium hydroxide and stearic ethanolic solution are mixed back ball milling 8 hours in high energy ball mill, the pulpous state presoma that obtains behind the ball milling is stirred in air to make its natural evaporation absolute ethyl alcohol mass percent extremely wherein be 50%.Presoma after natural evaporation is put into porcelain boat, push tube furnace, under argon gas atmosphere, 400
oC calcined 6 hours down, took out the gained solid with stove cooling back, through the levigate black powder shape product carbon cladded ferrous lithium phosphate that promptly obtains.
The mass percentage content of carbon is 10% in the present embodiment products therefrom, particle diameter 40～160 nm, and the charging and discharging capacity of following 50 circulations of 1C multiplying power is 150mAh/g (as shown in figure 15).
Mol ratio by iron and lithium is 1:1.05 weighing ferric phosphate and lithium hydroxide, takes by weighing stearic acid in the stearic ratio of every mole of phosphoric acid iron consumption 20g, and the stearic acid that takes by weighing is dissolved in the absolute ethyl alcohol, and being mixed with concentration is the stearic ethanolic solution of 10 g/L.Ferric phosphate, lithium hydroxide and stearic ethanolic solution are mixed back ball milling 8 hours in high energy ball mill, the pulpous state presoma that obtains behind the ball milling is stirred in air to make its natural evaporation absolute ethyl alcohol mass percent extremely wherein be 50%.Presoma after natural evaporation is put into porcelain boat, push tube furnace, under argon gas atmosphere, 400
oC calcined 6 hours down, took out the gained solid with stove cooling back, through the levigate black powder shape product carbon cladded ferrous lithium phosphate that promptly obtains.
The mass percentage content of carbon is 6% in the present embodiment products therefrom, particle diameter 40～160 nm, and the charging and discharging capacity of following 50 circulations of 1C multiplying power is 158 mAh/g.Figure 16 is the XRD figure spectrum of present embodiment products therefrom, and Figure 17 is the HRTEM figure of present embodiment products therefrom, and Figure 18 is the charging and discharging curve of present embodiment products therefrom under the 1C multiplying power.
Embodiment 11
Mol ratio by iron and lithium is 1:1 weighing ferric phosphate and lithium hydroxide, takes by weighing oleic acid in the ratio of every mole of phosphoric acid iron consumption 20g oleic acid, and the oleic acid that takes by weighing is dissolved in the absolute ethyl alcohol, is mixed with the ethanolic solution that concentration is the oleic acid of 10 g/L.The ethanolic solution of ferric phosphate, lithium hydroxide and oleic acid is mixed back ball milling 8 hours in high energy ball mill, the pulpous state presoma that obtains behind the ball milling is stirred in air to make the mass percent of its natural evaporation absolute ethyl alcohol extremely wherein be 50%.Presoma after natural evaporation is put into porcelain boat, push tube furnace, under argon gas atmosphere, 400
oC calcined 6 hours down, took out the gained solid with stove cooling back, through the levigate black powder shape product carbon cladded ferrous lithium phosphate that promptly obtains.
The mass percentage content of carbon is 6% in the present embodiment products therefrom, particle diameter 40～160 nm, and the charging and discharging capacity of following 50 circulations of 1C multiplying power is 157 mAh/g (as shown in figure 19).
Embodiment 12
Mol ratio by iron and lithium is 1:1 weighing ferric phosphate and lithium hydroxide, takes by weighing laurate in the lauric ratio of every mole of phosphoric acid iron consumption 20g, and the laurate that takes by weighing is dissolved in the absolute ethyl alcohol, and being mixed with concentration is the lauric ethanolic solution of 10 g/L.Ferric phosphate, lithium hydroxide and lauric ethanolic solution are mixed back ball milling 8 hours in high energy ball mill, the pulpous state presoma that obtains behind the ball milling is stirred in air to make the mass percent of its natural evaporation absolute ethyl alcohol extremely wherein be 50%.Presoma after natural evaporation is put into porcelain boat, push tube furnace, under argon gas atmosphere, 400
oC calcined 3 hours down, took out the gained solid with stove cooling back, through the levigate black powder shape product carbon cladded ferrous lithium phosphate that promptly obtains.
The mass percentage content of carbon is 6% in the present embodiment products therefrom, particle diameter 60～180 nm, and the charging and discharging capacity of following 50 circulations of 1C multiplying power is 156 mAh/g (as shown in figure 20).
Embodiment 13
Mol ratio by iron and lithium is 1:1 weighing ferric phosphate and lithium hydroxide, takes by weighing palmitic acid in the ratio of every mole of phosphoric acid iron consumption 20g palmitic acid, and the palmitic acid that takes by weighing is dissolved in the absolute ethyl alcohol, is mixed with the ethanolic solution that concentration is the palmitic acid of 10 g/L.The ethanolic solution of ferric phosphate, lithium hydroxide and palmitic acid is mixed back ball milling 8 hours in high energy ball mill, the pulpous state presoma that obtains behind the ball milling is stirred in air to make the mass percent of its natural evaporation absolute ethyl alcohol extremely wherein be 50%.Presoma after natural evaporation is put into porcelain boat, push tube furnace, under argon gas atmosphere, 400
oC calcined 6 hours down, took out the gained solid with stove cooling back, through the levigate black powder shape product carbon cladded ferrous lithium phosphate that promptly obtains.
The mass percentage content of carbon is 6% in the present embodiment products therefrom, particle diameter 40～160 nm, and the charging and discharging capacity of following 50 circulations of 1C multiplying power is 155 mAh/g (as shown in figure 21).
Embodiment 14
Mol ratio by iron and lithium is 1:1 weighing ferric phosphate and lithium carbonate, takes by weighing stearic acid in the stearic ratio of every mole of phosphoric acid iron consumption 20g, and the stearic acid that takes by weighing is dissolved in the absolute ethyl alcohol, and being mixed with concentration is the stearic ethanolic solution of 10 g/L.Ferric phosphate, lithium hydroxide and stearic ethanolic solution are mixed back ball milling 8 hours in high energy ball mill, the pulpous state presoma that obtains behind the ball milling is stirred in air to make the mass percent of its natural evaporation absolute ethyl alcohol extremely wherein be 50%.Presoma after natural evaporation is put into porcelain boat, push tube furnace, under argon gas atmosphere, 400
oC calcined 6 hours down, took out the gained solid with stove cooling back, through the levigate black powder shape product carbon cladded ferrous lithium phosphate that promptly obtains.
The mass percentage content of carbon is 6% in the present embodiment products therefrom, particle diameter 70～190 nm, and the charging and discharging capacity of following 50 circulations of 1C multiplying power is 152 mAh/g (as shown in figure 22).
Embodiment 15
Mol ratio by iron and lithium is 1:1 weighing ferric phosphate and lithium acetate, takes by weighing stearic acid in the stearic ratio of every mole of phosphoric acid iron consumption 20g, and the stearic acid that takes by weighing is dissolved in the absolute ethyl alcohol, and being mixed with concentration is the stearic ethanolic solution of 10 g/L.Ferric phosphate, lithium hydroxide and stearic ethanolic solution are mixed back ball milling 8 hours in high energy ball mill, the pulpous state presoma that obtains behind the ball milling is stirred in air to make the mass percent of its natural evaporation absolute ethyl alcohol extremely wherein be 50%.Presoma after natural evaporation is put into porcelain boat, push tube furnace, under argon gas atmosphere, 400
oC calcined 6 hours down, took out the gained solid with stove cooling back, through the levigate black powder shape product carbon cladded ferrous lithium phosphate that promptly obtains.
The mass percentage content of carbon is 6% in the present embodiment products therefrom, particle diameter 60～180 nm, and the charging and discharging capacity of following 50 circulations of 1C multiplying power is 150 mAh/g (as shown in figure 23).
Embodiment 16
Mol ratio by iron and lithium is 1:1 weighing ferric phosphate and lithium hydroxide, takes by weighing stearic acid in the stearic ratio of every mole of phosphoric acid iron consumption 20g, and the stearic acid that takes by weighing is dissolved in the acetone, and being mixed with concentration is the stearic acetone soln of 10 g/L.Ferric phosphate, lithium hydroxide and stearic acetone soln are mixed back ball milling 8 hours in high energy ball mill, the pulpous state presoma that obtains behind the ball milling is stirred in air to make the mass percent of its natural evaporation acetone extremely wherein be 50%.Presoma after natural evaporation is put into porcelain boat, push tube furnace, under argon gas atmosphere, 400
oC calcined 6 hours down, took out the gained solid with stove cooling back, through the levigate black powder shape product carbon cladded ferrous lithium phosphate that promptly obtains.
The mass percentage content of carbon is 6% in the present embodiment products therefrom, particle diameter 40～160 nm, and the charging and discharging capacity of following 50 circulations of 1C multiplying power is 158 mAh/g (as shown in figure 24).
Embodiment 17
With the carbon cladded ferrous lithium phosphate of embodiment 1-16 gained and conductive agent acetylene black, alite paste polytetrafluoroethylene (PTFE) ratio mixing, add the isopropyl alcohol of 20 times of quality (with respect to carbon cladded ferrous lithium phosphate and acetylene black gross mass) and the suspension (mass percent of PTFE is 27% in the suspension) of PTFE water then and make mixture in mass ratio 80:15:5; With the above-mentioned mixture that obtains 50
oAfter the C lower magnetic force is stirred to isopropyl alcohol and evaporates fully, take out the dried mixture powder and put into agate mortar, an amount of isopropyl alcohol to the mixture of dropping is the mud shape while grinding; With intensive drying after the mud shape mixture compacting film forming, the disk (about 6mg) of intercepting diameter 1.0mm places and is pressed into positive plate on the stainless (steel) wire.In the glove box that is full of Ar gas, be negative pole with the lithium sheet, with the LiPF of 1mol/L
6/ EC-EMC-DMC(1:1:1) be electrolyte, be assembled into 2016 type button cells, directly the charge-discharge performance of 2016 button cells of being assembled with blue electric battery measurement system testing.
Among the foregoing description 1-16, argon gas can be replaced by nitrogen, helium, can be replaced by other organic solvents as the absolute ethyl alcohol and the acetone of solvent, and the products therefrom performance is not had obvious influence.The particle diameter of the foregoing description products therefrom is by the acquisition of taking pictures of the Nova Nano SEM230 model ESEM of FEI Co..
Claims (7)
1. a low-temperature solid-phase method prepares the method for carbon cladded ferrous lithium phosphate positive electrode, it is characterized in that, may further comprise the steps:
1) mol ratio by iron and lithium is 1:(1 ~ 1.05) take by weighing ferric phosphate and lithium source, take by weighing aliphatic acid by every mole of phosphoric acid iron consumption 7.5 ~ 30g aliphatic acid again, the aliphatic acid that takes by weighing is dissolved in organic solvent, and ferric phosphate that adding takes by weighing in the organic solution of aliphatic acid and lithium source are after abundant mixed grinding obtains presoma;
2) with the presoma of step 1) gained in non-oxidizing atmosphere, in 400 ~ 700
oC is calcining 0.5 ~ 12h down, promptly obtains the carbon cladded ferrous lithium phosphate positive electrode after the cooling.
2. low-temperature solid-phase method according to claim 1 prepares the method for carbon cladded ferrous lithium phosphate positive electrode, it is characterized in that: before calcining described presoma stirred in air and make its natural evaporation to the mass percent of organic solvent wherein be not more than 60%.
3. low-temperature solid-phase method according to claim 1 prepares the method for carbon cladded ferrous lithium phosphate positive electrode, it is characterized in that: described ferric phosphate, lithium source are nanoscale.
4. low-temperature solid-phase method according to claim 1 prepares the method for carbon cladded ferrous lithium phosphate positive electrode, it is characterized in that: described lithium source is single thing or the composition more than two in lithium hydroxide, lithium carbonate, the lithium acetate.
5. low-temperature solid-phase method according to claim 1 prepares the method for carbon cladded ferrous lithium phosphate positive electrode, it is characterized in that: described aliphatic acid is single thing or the composition more than two in stearic acid, oleic acid, laurate, the palmitic acid.
6. low-temperature solid-phase method according to claim 1 prepares the method for carbon cladded ferrous lithium phosphate positive electrode, it is characterized in that: described non-oxidizing atmosphere is single thing or its both composition in nitrogen, argon gas, the helium.
7. low-temperature solid-phase method according to claim 1 prepares the method for carbon cladded ferrous lithium phosphate positive electrode, it is characterized in that: described organic solvent is alcohol or acetone.
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| CN105206840A (en) * | 2015-08-18 | 2015-12-30 | 合肥国轩高科动力能源有限公司 | Method for synthesizing lithium battery anode material by solvent-free solid phase method |
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| CN101969118A (en) * | 2010-10-13 | 2011-02-09 | 武汉大学 | Method for synthesizing carbon-coated lithium iron phosphate of lithium ion battery cathode material |
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| CN106328899A (en) * | 2016-10-11 | 2017-01-11 | 苏州大学 | Nano ternary cathode material and preparation method thereof |
| CN106328899B (en) * | 2016-10-11 | 2019-06-21 | 苏州大学 | Nano ternary cathode material and preparation method thereof |
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| CN108183216B (en) * | 2017-12-28 | 2020-10-09 | 国联汽车动力电池研究院有限责任公司 | Carbon-coated lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery |
| CN111554907A (en) * | 2020-05-15 | 2020-08-18 | 深圳澳睿新能源科技有限公司 | Application of fatty acid in preparation of lithium ion battery and method for preparing electrode material |
| CN111554907B (en) * | 2020-05-15 | 2022-08-05 | 深圳澳睿新能源科技有限公司 | Application of fatty acid in preparation of lithium ion battery and method for preparing electrode material |
| CN112897584A (en) * | 2021-01-21 | 2021-06-04 | 湘潭大学 | Lithium-rich manganese-based cathode material with divalent cations doped in lithium layer and preparation method thereof |
| CN114927682A (en) * | 2022-05-18 | 2022-08-19 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | LiNi ternary material for increasing high nickel content x Co y Mn 1-x-y O 2 Method for cycling stability and safety of anode material |
| CN115304046A (en) * | 2022-09-08 | 2022-11-08 | 四川大学 | Sodium vanadium phosphate, sodium vanadium manganese phosphate and preparation method thereof |
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