CN107658461B - Method for preparing ferric fluoride/carbon composite material by taking organic iron compound as raw material - Google Patents
Method for preparing ferric fluoride/carbon composite material by taking organic iron compound as raw material Download PDFInfo
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Abstract
The invention discloses a method for preparing a ferric fluoride/carbon composite material by taking an organic iron compound as a raw material. The invention takes an organic iron compound as a raw material, firstly obtains a precursor with the main components of simple substance iron and carbon through high-temperature carbonization, and then treats the precursor through hydrogen fluoride steam to ensure that the simple substance iron and hydrogen fluoride completely react to obtain the ferric fluoride/carbon composite material. The raw materials adopted in the invention belong to organic iron sources, which is beneficial to the in-situ carbon modification of uniform dispersion of ferric fluoride in the composite material, improves the conductivity of the material, and shows good electrochemical performance when being used as the anode material of the lithium ion battery. The raw materials used in the invention are cheap and easy to obtain, and the preparation process is simple, and the method has wide application prospect in the fields of preparation of lithium ion battery materials and the like.
Description
Technical Field
The invention belongs to the field of preparation of lithium ion battery anode materials, and particularly relates to a method for preparing a fluoride/carbon composite material by taking an organic iron compound as a raw material.
Background
The lithium ion battery is a novel energy storage device which is rapidly developed in recent years, has the advantages of high storage energy density, long service life, low self-discharge rate and environmental protection, and is widely applied to the fields of portable electronic equipment, electric vehicles and the like. However, in the production of lithium ion batteries, the conventional cathode material has the problem of lower theoretical capacity, and in addition, the battery manufacturing cost is higher due to the large amount of cobalt used in the cathode material, so that the current situation is difficult to meet the urgent requirements of people on high energy and low price of the lithium ion batteries. Therefore, it is significant to develop a new high-capacity, low-cost lithium ion cathode material or a new class of alternative lithium ion cathode materials with practical application potential.
The specific capacity of the traditional anode material is limited by an intercalation and deintercalation lithium mechanism, and only 0.5-1 equivalent of lithium ions are subjected to deintercalation reaction in the electrode reaction process, so that the high-capacity lithium ion battery anode material needs to have the characteristic of multi-electron reaction. The electrode materials capable of realizing the reaction of participation of multiple electrons are mainly transition metal compounds, such as: fluoride, oxide, sulfide, nitride (MeXy, X is F, O, S, N), and the like, wherein the ferric fluoride has a relatively high theoretical specific capacity due to a relatively high voltage platform, and has the advantages of low cost, low toxicity, environmental friendliness, good thermal stability, and the like, thereby becoming a research hotspot of the ferric fluoride anode material. However, iron fluoride has problems such as poor conductivity, unstable structure, and pulverization of the material.
Aiming at the problems of the ferric fluoride anode material, the most common technical scheme is to adopt a carbon compounding method at present, improve the conductivity of the composite material and relieve the problems of volume expansion and pulverization of the electrode material by coating a conductive carbon material on the surface of the ferric fluoride. For example, Yong Kyung Kim et al, university of east Asia, Japan, intercalates iron fluoride into porous carbon (Journal of Physical Chemistry C.2013,119(29): 14939-; FeF by Sung-Wook Kim et al, Korea institute of science and technology3In situ growth on carbon nanotubes (advanced materials 2010,22(46): 5260-; ruguang Ma and the like of hong Kong university prepare FeF by utilizing excellent conductivity of graphene3Graphene composite (nanoscale.2013,5(14): 6338-; t.kim et al of east asia university wraps graphitized carbon around FeF3(journal of Physical Chemistry A.2016,4(38): 14857-14864). Generally, the specific capacity and the cycle performance of the composite material can be improved to a certain extent by means of compounding the iron fluoride and the carbon material, but the preparation process is generally complex, the required temperature is low, and a complete carbon coating layer is difficult to prepare, so that the iron fluoride and the carbon are difficult to disperse uniformly, expensive raw materials such as carbon nanotubes and graphene are often involved, and the composite material is not favorable for commercial use.
Disclosure of Invention
The invention provides a method for preparing a fluoride/carbon composite material by taking an organic iron compound as a raw material, aiming at the technical problem of preparation of a fluoride cathode material.
The invention relates to a method for preparing a ferric fluoride/carbon composite material by taking an organic iron compound as a raw material, which comprises the following steps:
step one
Putting organic iron compound powder into an alumina crucible, and carrying out carbonization treatment for 1-3 h at 600-900 ℃ under a protective atmosphere to obtain an iron-carbon compound;
step two
And (3) treating the iron-carbon composite obtained in the step one in hydrogen fluoride steam at the temperature of 50-200 ℃ for 12-72 h, washing and drying to obtain the iron fluoride/carbon composite material.
In the first step, the number of carbon in the carbon chain of the organic moiety in the organic iron compound is preferably 5 to 100.
Preferably, in the first step, the organic iron compound is one of ferric citrate, ferric oxalate, ferrocene, ferrous lactate, ferric glycinate, ferric stearate, and the like. Preferably ferric citrate.
In the first step, the protective atmosphere is preferably an argon atmosphere.
Preferably, in the first step, the carbonization temperature is 695-705 ℃, more preferably 700 ℃, and the carbonization time is 110-130 min, more preferably 2 h.
Preferably, in the first step, the temperature is increased to 600-900 ℃ at a temperature increase rate of 3-8 ℃/min.
In the second step, hydrogen fluoride is heated to 50-200 ℃, preferably 50-70 ℃ to generate hydrogen fluoride steam, then the hydrogen fluoride steam is sent to the iron-carbon composite for reaction, and the reaction temperature is controlled to be 50-200 ℃, preferably 50-70 ℃; obtaining the ferric fluoride/carbon composite material. In practical application, the iron-carbon composite can be placed in a plastic container.
Preferably, in the second step, hydrogen fluoride is heated to 50-200 ℃, preferably 50-70 ℃, and more preferably 60-70 ℃ to generate hydrogen fluoride steam, and then the hydrogen fluoride steam is sent to the iron-carbon composite for reaction, wherein the reaction temperature is controlled to be 50-200 ℃, preferably 50-70 ℃, and more preferably 60-70 ℃, and the reaction time is 30-40 hours, and preferably 35-37 hours; obtaining the ferric fluoride/carbon composite material.
Further, in the second step, the vapor temperature of the hydrogen fluoride is preferably 60 ℃ and the treatment time is preferably 36 hours.
Further, in the second step, the specific steps of washing and drying are as follows: and repeatedly washing the reaction product with absolute ethyl alcohol, and drying the obtained product in a drying oven at the temperature of 80 ℃ for more than 12 hours.
The iron fluoride/carbon composite material prepared by the invention is particularly suitable for being used as a lithium ion battery anode material.
In the invention, when the organic iron compound is selected, particularly ferric citrate is used as a carbon source and an iron source, the carbonization temperature is preferably 695-705 ℃, the temperature of hydrogen fluoride steam is preferably 60 ℃, and the treatment time of the hydrogen fluoride steam is 35-37h, the performance of the obtained product is far better than that of the product obtained by other schemes of the invention.
After the treatment of the optimized scheme, preparing the iron fluoride/carbon composite material prepared by the invention, conductive carbon black and a binder (PVDF) into slurry according to the mass ratio of 8:1:1, coating the slurry on an aluminum foil, and drying the aluminum foil at 120 ℃ for 24 hours to prepare a lithium ion battery positive pole piece; a button lithium battery CR2025 is used as a simulation battery, a metal lithium sheet is used as a counter electrode, and the electrolyte composition is 1M LiPF6(ethylene carbonate: diethyl carbonate ═ 1:1, v/v), septum Celgard2400, assembled in a glove box filled with argon; the prepared battery completes the charge and discharge test at the current density of 40mA/g and the charge and discharge interval of 1.5-4.5V, the active substance is calculated by the content of ferric fluoride, the first reversible specific capacity is 430mAh/g at the current density of 40mA/g, and the capacity is still kept at 180mAh/g after 100 cycles of charge and discharge.
The principle and the characteristics of the invention are as follows: the invention takes an organic iron compound as a raw material, firstly decomposes the organic iron compound under a proper high-temperature condition, reduces an iron element in the decomposition process to generate simple substance iron, converts a carbon element into carbon while reducing the iron element to obtain an iron-carbon compound with uniform dispersion, then reacts the simple substance iron in the compound with hydrogen fluoride to generate an iron fluoride electrode material capable of performing electrochemical energy storage through hydrogen fluoride steam treatment, and simultaneously forms in-situ coating on the generated iron fluoride by the carbon component uniformly dispersed in the compound to finally prepare the iron fluoride/carbon composite material with stable structure and tight combination.
The iron fluoride/carbon composite material prepared by the invention has the following beneficial effects:
(1) the preparation method, especially the optimized preparation method, can realize the uniform and complete coating effect of the conductive carbon on the ferric fluoride particles, ensure that the ferric fluoride has extremely high reaction activity, effectively solve the problem of poor conductivity of the ferric fluoride, relieve the volume expansion of the ferric fluoride, inhibit the pulverization of electrode materials and improve the electrochemical performance of the ferric fluoride.
(2) In the preparation process of the invention, the thickness of the carbon layer coated on the surface of the ferric fluoride can be adjusted by controlling the carbonization temperature and the carbonization time.
(3) The organic iron compound used as the raw material in the invention, such as ferric citrate, has low price and the characteristics of wide source and no toxicity. The preparation method adopted by the invention is simple to operate, easy to control, green and environment-friendly, and is beneficial to the commercial development and application of the lithium ion battery anode material.
Drawings
Fig. 1 is an XRD pattern of the sample after ferric citrate charring and ferric fluoride/carbon composite of example 1 of the present invention;
FIG. 2 is a thermogravimetric analysis of the iron fluoride/carbon composite prepared in example 1;
FIG. 3 is an SEM image of an iron fluoride/carbon composite prepared in example 1 of the present invention;
fig. 4 is a constant current discharge cycle performance diagram of the iron fluoride/carbon composite material prepared in example 1 of the present invention.
From FIG. 1, it can be seen that the main phase component of the carbonized product is Fe. The main material phase component of the product of the iron/carbon composite treated by HF acid is Fe2F5·2H2O。
From fig. 2 it can be seen that the carbon content in the composite is 2.9%.
It can be seen from fig. 3 that the composite material exhibits irregular mass.
As can be seen from FIG. 4, the first reversible specific capacity is 440mAh/g at a current density of 40mA/g, and the capacity is still maintained at 180mAh/g after 100 cycles of charge and discharge.
Detailed Description
The following examples illustrate specific steps of the present invention, but are not intended to limit the invention.
Terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art, unless otherwise specified.
The present invention is described in further detail below with reference to specific examples and with reference to the data. It will be understood that these examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
In the following examples, various procedures and methods not described in detail are conventional methods well known in the art.
The present invention is further illustrated by the following specific examples.
Example 1
The method comprises the following steps:
(1) putting a certain amount of ferric citrate into a tubular furnace filled with argon for carbonization treatment at 700 ℃ for 2h to obtain an iron/carbon compound;
(2) putting the iron/carbon composite into hydrogen fluoride steam, wherein the steam temperature is 60 ℃, and keeping the temperature for 36 h.
(3) And (3) washing the reaction product in the step (2) by using absolute ethyl alcohol, and then drying the reaction product in a drying oven to obtain the ferric fluoride/carbon composite material (figure 3).
(4) And (4) carrying out a simulated battery performance test on the product obtained in the step (3).
And (3) preparing the prepared composite material, conductive carbon black and a binder (PVDF) into slurry according to the mass ratio of 8:1:1, coating the slurry on an aluminum foil, and drying the aluminum foil at 120 ℃ for 24 hours to prepare the lithium ion battery positive pole piece. A button lithium battery CR2025 is used as a simulation battery, a metal lithium sheet is used as a counter electrode, and the electrolyte composition is 1MLiPF6(ethylene carbonate: diethyl carbonate ═ 1:1, v/v), septum Celgard2400, assembled in a glove box filled with argon. The prepared battery completes the charge and discharge test at the current density of 40mA/g and the charge and discharge interval of 1.5-4.5V, and the active substance is calculated by the content of ferric fluoride. FIG. 4 shows the constant current charging and discharging of the prepared iron fluoride/carbon composite materialThe electric cycle performance diagram shows that under the current density of 40mA/g, the first reversible specific capacity is 430mAh/g, and the capacity is still kept at 180mAh/g after 100 cycles of charge and discharge;
example 2
The preparation method is the same as that of example 1, except that the carbonization temperature in the step (1) of example 1 is changed to 600 ℃, and the phase characterization shows that the obtained product is the ferric fluoride/carbon composite material.
The prepared material is prepared into a positive pole piece of the lithium ion battery according to the method of the embodiment 1, and the simulated battery is assembled. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 410mAh/g, and the reversible specific capacity after 100 cycles is 160 mAh/g.
Example 3
The preparation method is the same as that of example 1, except that the carbonization temperature in the step (1) of example 1 is changed to 800 ℃, and the phase characterization shows that the obtained product is the ferric fluoride/carbon composite material.
The prepared material is prepared into a positive pole piece of the lithium ion battery according to the method of the embodiment 1, and the simulated battery is assembled. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 397mAh/g, and the reversible specific capacity after 100 cycles is 155 mAh/g.
Example 4
The preparation method is the same as that of example 1, except that the carbonization temperature in the step (1) of example 1 is changed to 900 ℃, and the phase characterization shows that the obtained product is the ferric fluoride/carbon composite material.
The prepared material is prepared into a positive pole piece of the lithium ion battery according to the method of the embodiment 1, and the simulated battery is assembled. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 380mAh/g, and the reversible specific capacity after 100 cycles is 140 mAh/g.
Example 5
The preparation method is the same as example 1 except that the carbonization time in the step (1) of the example 1 is changed into 1h, and the phase characterization shows that the obtained product is the ferric fluoride/carbon composite material.
The prepared material is prepared into a positive pole piece of the lithium ion battery according to the method of the embodiment 1, and the simulated battery is assembled. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 405 mAh/g, and the reversible specific capacity after 100 cycles is 148 mAh/g.
Example 6
The preparation method is the same as example 1 except that the carbonization time in the step (1) of example 1 is changed to 3 hours, and the phase characterization shows that the obtained product is the ferric fluoride/carbon composite material.
The prepared material is prepared into a positive pole piece of the lithium ion battery according to the method of the embodiment 1, and the simulated battery is assembled. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 420mAh/g, and the reversible specific capacity after 100 cycles is 130 mAh/g.
Example 7
The preparation method is the same as that of example 1, except that the temperature of the hydrogen fluoride steam in the step (1) of example 1 is changed to 50 ℃, and phase characterization shows that the obtained product is the ferric fluoride/carbon composite material.
The prepared material is prepared into a positive pole piece of the lithium ion battery according to the method of the embodiment 1, and the simulated battery is assembled. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 410mAh/g, and the reversible specific capacity after 100 cycles is 160 mAh/g.
Example 8
The preparation method is the same as that of example 1, except that the temperature of the hydrogen fluoride steam in the step (1) of example 1 is changed to 70 ℃, and phase characterization shows that the obtained product is the ferric fluoride/carbon composite material.
The prepared material is prepared into a positive pole piece of the lithium ion battery according to the method of the embodiment 1, and the simulated battery is assembled. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 420mAh/g, and the reversible specific capacity after 100 cycles is 170 mAh/g.
Example 9
The preparation method is the same as that of example 1, except that the temperature of the hydrogen fluoride steam in the step (1) of example 1 is changed to 90 ℃, and phase characterization shows that the obtained product is the ferric fluoride/carbon composite material.
The prepared material is prepared into a positive pole piece of the lithium ion battery according to the method of the embodiment 1, and the simulated battery is assembled. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 400mAh/g, and the reversible specific capacity after 100 cycles is 140 mAh/g.
Example 10
The preparation method is the same as that of example 1, except that the temperature of the hydrogen fluoride steam in the step (1) of example 1 is changed to 120 ℃, and phase characterization shows that the obtained product is the ferric fluoride/carbon composite material.
The prepared material is prepared into a positive pole piece of the lithium ion battery according to the method of the embodiment 1, and the simulated battery is assembled. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 370mAh/g, and the reversible specific capacity after 100 cycles is 116 mAh/g.
Example 11
The preparation method is the same as that of example 1, except that the temperature of the hydrogen fluoride steam in the step (1) of example 1 is changed to 150 ℃, and phase characterization shows that the obtained product is the ferric fluoride/carbon composite material.
The prepared material is prepared into a positive pole piece of the lithium ion battery according to the method of the embodiment 1, and the simulated battery is assembled. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 330mAh/g, and the reversible specific capacity after 100 cycles is 100 mAh/g.
Example 12
The preparation method is the same as that of example 1, except that the temperature of the hydrogen fluoride steam in the step (1) of example 1 is changed to 180 ℃, and phase characterization shows that the obtained product is the ferric fluoride/carbon composite material.
The prepared material is prepared into a positive pole piece of the lithium ion battery according to the method of the embodiment 1, and the simulated battery is assembled. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 300mAh/g, and the reversible specific capacity after 100 cycles is 85 mAh/g.
Example 13
The preparation method is the same as that of example 1, except that the temperature of the hydrogen fluoride steam in the step (1) of example 1 is changed to 200 ℃, and phase characterization shows that the obtained product is the ferric fluoride/carbon composite material.
The prepared material is prepared into a positive pole piece of the lithium ion battery according to the method of the embodiment 1, and the simulated battery is assembled. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 270mAh/g, and the reversible specific capacity after 100 cycles is 60 mAh/g.
Example 13
The preparation method is the same as that of example 1, except that the hydrogen fluoride steam heat preservation time in the step (1) of example 1 is changed into 12 hours, and the phase characterization shows that the obtained product is the ferric fluoride/carbon composite material.
The prepared material is prepared into a positive pole piece of the lithium ion battery according to the method of the embodiment 1, and the simulated battery is assembled. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 350mAh/g, and the reversible specific capacity after 100 cycles is 146 mAh/g.
Example 14
The preparation method is the same as that of example 1, except that the temperature holding time of the hydrogen fluoride steam in the step (1) of example 1 is changed to 24 hours, and phase characterization shows that the obtained product is the ferric fluoride/carbon composite material.
The prepared material is prepared into a positive pole piece of the lithium ion battery according to the method of the embodiment 1, and the simulated battery is assembled. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 390mAh/g, and the reversible specific capacity after 100 cycles is 160 mAh/g.
Example 15
The preparation method is the same as that of example 1, except that the temperature holding time of the hydrogen fluoride steam in the step (1) of example 1 is changed to 48 hours, and phase characterization shows that the obtained product is the ferric fluoride/carbon composite material.
The prepared material is prepared into a positive pole piece of the lithium ion battery according to the method of the embodiment 1, and the simulated battery is assembled. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 380mAh/g, and the reversible specific capacity after 100 cycles is 156 mAh/g.
Example 16
The preparation method is the same as that of example 1, except that the hydrogen fluoride steam heat preservation time in the step (1) of example 1 is changed into 60 hours, and the phase characterization shows that the obtained product is the ferric fluoride/carbon composite material.
The prepared material is prepared into a positive pole piece of the lithium ion battery according to the method of the embodiment 1, and the simulated battery is assembled. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 320mAh/g, and the reversible specific capacity after 100 cycles is 132 mAh/g.
Example 17
The preparation method is the same as that of example 1, except that the hydrogen fluoride steam heat preservation time in the step (1) of example 1 is changed to 72 hours, and the phase characterization shows that the obtained product is the ferric fluoride/carbon composite material.
The prepared material is prepared into a positive pole piece of the lithium ion battery according to the method of the embodiment 1, and the simulated battery is assembled. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 260mAh/g, and the reversible specific capacity after 100 cycles is 96 mAh/g.
Example 18
The preparation method is the same as that of example 1, except that the ferric citrate in the step (1) of example 1 is changed into ferric oxalate, and the phase characterization shows that the obtained product is ferric fluoride/carbon composite material.
The prepared material is prepared into a positive pole piece of the lithium ion battery according to the method of the embodiment 1, and the simulated battery is assembled. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 260mAh/g, and the reversible specific capacity after 100 cycles is 106 mAh/g.
Example 19
The preparation method is the same as example 1 except that the ferric citrate in the step (1) of example 1 is changed into ferrocene, and phase characterization shows that the obtained product is a ferric fluoride/carbon composite material.
The prepared material is prepared into a positive pole piece of the lithium ion battery according to the method of the embodiment 1, and the simulated battery is assembled. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 275mAh/g, and the reversible specific capacity after 100 cycles is 109 mAh/g.
Comparative example 1
(1) Putting a certain amount of iron powder into hydrogen fluoride steam, wherein the steam temperature is 60 ℃, and keeping the temperature for 36 h.
(2) And (3) drying the reaction product in the step (1) in a drying box to obtain a solid powder electrode product.
(3) And (3) carrying out a simulated battery performance test on the product in the step (2).
And (3) preparing the prepared material, conductive carbon black and a binder (PVDF) into slurry according to the mass ratio of 8:1:1, coating the slurry on an aluminum foil, and drying the aluminum foil at 120 ℃ for 24 hours to prepare the lithium ion battery positive pole piece. A button lithium battery CR2025 is used as a simulation battery, a metal lithium sheet is used as a counter electrode, and the electrolyte composition is 1M LiPF6(ethylene carbonate: diethyl carbonate ═ 1:1, v/v), septum Celgard2400, assembled in a glove box filled with argon. The prepared battery completes the charge and discharge test at the current density of 40mA/g and the charge and discharge interval of 1.5-4.5V, and the active substance is calculated by the content of ferric fluoride. The first reversible specific capacity of the battery is 230mAh/g, and the reversible specific capacity after 100 cycles is 110 mAh/g.
Comparative example 2
The preparation method is the same as that of comparative example 1 except that the raw material in step (1) of comparative example 1 is changed into ferric oxide.
And (3) preparing the prepared material into a lithium ion battery positive pole piece according to the method of the comparative example 1, and assembling the simulated battery. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 190mAh/g, and the reversible specific capacity after 100 cycles is 50 mAh/g.
Comparative example 3:
the preparation method is the same as that of example 1, except that the hydrogen fluoride vapor treatment in step (2) of example 1 is changed to the hydrogen fluoride solution treatment.
And (3) preparing the prepared material into a lithium ion battery positive pole piece according to the method of the comparative example 1, and assembling the simulated battery. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 58mAh/g, and the reversible specific capacity after 100 cycles is 25 mAh/g.
It can thus be seen that: the iron-carbon composite can not be directly placed in a hydrogen fluoride solution and is subjected to heating treatment at 50-200 ℃. It is because it is possible to: when the iron-carbon composite is placed in a hydrogen fluoride solution, iron is dissolved in the hydrogen fluoride solution and is lost, and only carbon remains, so that the iron fluoride/carbon composite material cannot be obtained.
Comparative example 4:
the preparation method is the same as that of example 1, except that the ferric citrate in the step (1) of example 1 is changed into glucose and iron powder mixture with equal mass (the amount of the ferric substance is completely consistent).
And (3) preparing the prepared material into a lithium ion battery positive pole piece according to the method of the comparative example 1, and assembling the simulated battery. The prepared battery completes the charge and discharge test in a charge and discharge interval of 1.5-4.5V under the current density of 40 mA/g. The first reversible specific capacity of the battery is 235mAh/g, and the reversible specific capacity after 100 cycles is 104 mAh/g.
Claims (6)
1. A method for preparing ferric fluoride/carbon composite material by taking organic iron compound as raw material is characterized in that: comprises the following steps;
step one
Putting organic iron compound powder into an alumina crucible, and carrying out carbonization treatment for 110-130 min at 695-705 ℃ under a protective atmosphere to obtain an iron-carbon compound; in the first step, the organic iron compound is one of ferric citrate, ferric oxalate, ferrocene, ferrous lactate, ferric glycinate and ferric stearate;
step two
Heating hydrogen fluoride to 50-70 ℃ to generate hydrogen fluoride steam, then sending the hydrogen fluoride steam to the iron-carbon composite for reaction, controlling the reaction temperature to be 50-70 ℃, reacting for 35-37h, washing and drying to obtain the iron fluoride/carbon composite material.
2. The method for preparing the ferric fluoride/carbon composite material by using the organic iron compound as the raw material according to claim 1, wherein the method comprises the following steps: in the first step, the protective atmosphere is argon atmosphere.
3. The method for preparing the ferric fluoride/carbon composite material by using the organic iron compound as the raw material according to claim 1, wherein the method comprises the following steps: in the first step, the carbonization temperature is 700 ℃, and the carbonization time is 2 hours.
4. The method for preparing the ferric fluoride/carbon composite material by using the organic iron compound as the raw material according to claim 1, wherein the method comprises the following steps: in the second step, the temperature of the hydrogen fluoride steam is 60 ℃, the reaction temperature is 60 ℃ and the reaction time is 36 hours.
5. The method for preparing the ferric fluoride/carbon composite material by using the organic iron compound as the raw material according to claim 1, wherein the method comprises the following steps: in the second step, the concrete steps of washing and drying are as follows: and repeatedly washing the reaction product with absolute ethyl alcohol, and drying the obtained product in a drying oven at the temperature of 80 ℃ for more than 12 hours.
6. The method for preparing the ferric fluoride/carbon composite material by using the organic iron compound as the raw material according to any one of claims 1 to 5, wherein the method comprises the following steps: the prepared ferric fluoride/carbon composite material is used as a lithium ion battery anode material.
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| CN112701286A (en) * | 2020-12-28 | 2021-04-23 | 中国科学院过程工程研究所 | Ferric fluoride/carbon composite positive electrode material, preparation method thereof and lithium ion battery |
| CN114447318B (en) * | 2021-12-22 | 2023-07-25 | 西安理工大学 | Preparation method for synthesizing ferric trifluoride carbon anode material by gas phase fluorination |
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| CN102315482A (en) * | 2011-08-31 | 2012-01-11 | 北京理工大学 | Lithium secondary battery with metal fluoride as positive electrode material |
| CN104091949A (en) * | 2014-07-16 | 2014-10-08 | 北京化工大学常州先进材料研究院 | Charcoal-coated metal fluoride nano material with core-shell structure, preparation method and application of nano material as lithium battery positive electrode material |
| CN105336946A (en) * | 2015-09-28 | 2016-02-17 | 中国船舶重工集团公司第七一二研究所 | Preparation method of ferric fluoride cathode material for lithium ion battery |
| CN106356528A (en) * | 2015-07-18 | 2017-01-25 | 宁波大学 | Ferric fluoride electrode material for energy storage and preparation method thereof |
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| CN102315482A (en) * | 2011-08-31 | 2012-01-11 | 北京理工大学 | Lithium secondary battery with metal fluoride as positive electrode material |
| CN104091949A (en) * | 2014-07-16 | 2014-10-08 | 北京化工大学常州先进材料研究院 | Charcoal-coated metal fluoride nano material with core-shell structure, preparation method and application of nano material as lithium battery positive electrode material |
| CN106356528A (en) * | 2015-07-18 | 2017-01-25 | 宁波大学 | Ferric fluoride electrode material for energy storage and preparation method thereof |
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