CN110627078A - Method for preparing negative electrode material by modifying biotite through lithium ion exchange method - Google Patents

Method for preparing negative electrode material by modifying biotite through lithium ion exchange method Download PDF

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CN110627078A
CN110627078A CN201911045876.7A CN201911045876A CN110627078A CN 110627078 A CN110627078 A CN 110627078A CN 201911045876 A CN201911045876 A CN 201911045876A CN 110627078 A CN110627078 A CN 110627078A
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biotite
electrode material
negative electrode
ion exchange
lepidolite
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CN110627078B (en
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黄志良
程怡林
姚东辉
吴昌胜
陈松
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Wuhan Institute of Technology
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Wuhan Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/42—Micas ; Interstratified clay-mica products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties

Abstract

The invention relates to a method for preparing a negative electrode material by modifying biotite through a lithium ion exchange method, wherein the negative electrode material is hydrated lepidolite and is prepared by replacing potassium ions in the biotite with lithium ions. The method for extracting the potassium ions by using the lithium ion exchange method has the advantages of low extraction cost, high speed and environmental friendliness, retains the typical layered structure of the biotite, obviously improves the specific capacitance of the prepared cathode material, has low price of the biotite, reduces the preparation cost of the electrode material, provides a plurality of choices for the development of the electrode material, and has wide application prospect.

Description

Method for preparing negative electrode material by modifying biotite through lithium ion exchange method
Technical Field
The invention relates to the technical fields of chemistry, new energy development and the like, in particular to a method for preparing a negative electrode material by modifying biotite through a lithium ion exchange method.
Technical Field
Biotite as a mineral of the mica group having a typical layered silicate structure, in the crystal structure of the mica group, [ SiO ]4]Tetrahedral layer and [ AlO ]6]The ratio of the octahedral layer is 1: 2, SiO in mica structural unit layer4]The obvious Al-Si substitution phenomenon exists in the tetrahedral sheet layer, which becomes 'isomorphism substitution' in the mineralogy, which causes that the structural unit layer has a large amount of negative charges, and the layers need to absorb the same amount of positive charges and cations, thereby realizing that the mica is integrally electrifiedAnd (4) the product is neutral. The biotite ore has abundant reserves, low price, excellent physical and chemical properties and wide application and research, and is mainly applied to the building material industry, the fire-fighting industry, the fire extinguishing agent, the plastic, the papermaking and other chemical industries. In the field of plastics industry, biotite is mainly used as a filler, which can increase strength and improve a series of properties of plastic products, including heat resistance and dimensional stability. The biotite has a typical layered structure, is very similar to the layered structure of a graphene negative electrode material, and has the potential of being used as an electrode material, but the biotite has poor electrical properties and cannot be directly used as the electrode material, so that a simple and effective method for modifying the biotite is required to be found, and the biotite is used in a battery electrode.
Disclosure of Invention
The invention mainly aims to provide a method for preparing a negative electrode material by modifying biotite through a lithium ion exchange method. The cathode material obtained by the method has good electrochemical performance, low cost and environmental friendliness, and has wide application prospects in the fields of novel solid batteries, chemical sensors, electrode materials and the like.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the method for preparing the negative electrode material by modifying the biotite through the lithium ion exchange method is provided, the negative electrode material is hydrated lepidolite, and the negative electrode material is prepared by replacing potassium ions in the biotite with lithium ions.
According to the scheme, the method specifically comprises the following steps:
1) pulverizing biotite ore and sieving;
2) mixing the biotite obtained in the step 1) with an aqueous solution of a soluble lithium salt, adding an acid solution to adjust the mixed solution to be acidic, heating for reaction, filtering and drying to obtain the hydrated lepidolite negative electrode material.
According to the scheme, the biotite ore in the step 1) is crushed and then passes through a 200-mesh screen.
According to the scheme, the acid solution is added before the reaction in the step 2) to adjust the pH value of the mixed solution to 1.3-1.5.
According to the scheme, the concentration of the soluble lithium salt aqueous solution in the step 2) is 0.77-0.80mol/L, and the mass-volume ratio of the biotite to the soluble lithium salt aqueous solution is 1 g: 245-250 ml.
According to the scheme, the soluble lithium salt in the step 2) is lithium nitrate.
According to the scheme, the acid solution in the step 2) is dilute hydrochloric acid, and the concentration is 0.4-0.6 mol/L.
According to the scheme, the heating reaction conditions in the step 2) are as follows: the temperature is 70-80 ℃, and the reaction time is 5-10 h; preferably, the reaction temperature is 80 ℃ and the reaction time is 8-10 h.
According to the invention, the negative electrode material is prepared by modifying the biotite through a lithium ion exchange method, and the biotite is modified through the lithium ion exchange method, on one hand, potassium ions and lithium ions are located in the same main group of the periodic table of elements, the structure and the property of the biotite are similar, the radius ratio of the lithium ions is smaller, the biotite can enter into the layers of the biotite more easily to hydrolyze and exchange with the potassium ions, the biotite becomes hydrated lithium ions after hydrolysis, the ion radius is larger, the constraint of the layers on the potassium ions is smaller, and the potassium ions can be replaced more easily; the lithium ions are monovalent ions, one lithium ion can replace one potassium ion, and for the divalent ions, one divalent ion can replace two potassium ions, compared with the divalent ions, the number of hydrated lithium ions entering the interlayer is more, more storage sites can be provided for electrons, the storage and release of the electrons are facilitated, and the energy density of the cathode material is improved.
The invention has the beneficial effects that:
1. the hydrated lepidolite negative electrode material is prepared by extracting potassium ions by using a lithium ion exchange method, has low extraction cost, high speed and environmental friendliness, retains the typical layered structure of the biotite, obviously improves the obtained negative electrode material compared with the capacitance, and has wide application prospect in the fields of novel solid batteries, chemical sensors, electrode materials and the like.
2. According to the invention, lithium ions are used for exchanging potassium ions in the biotite, the lithium ions are monovalent, and compared with divalent ions, more hydrated lithium ions are used for carrying out interlamination of the biotite, so that more storage sites are provided for electrons, the storage and release of the electrons are facilitated, and the specific capacitance of the cathode material is improved.
3. The biotite ore has abundant reserves and low price, and the modified biotite is used in the electrode material, so that the preparation cost of the electrode material is reduced, and the electrode material has wide application prospects.
4. The biotite has a typical layered structure similar to graphene and has the potential of being used as an electrode material, and the invention provides a plurality of options for the development of the electrode material by modifying the biotite to be used in the electrode material.
Drawings
Fig. 1 is an XRD pattern of biotite raw ore.
FIG. 2 is a cyclic charge and discharge curve of raw biotite at a current density of 0.2A/g.
Fig. 3 is an XRD pattern of the hydrous lepidolite anode material prepared in example 1.
FIG. 4 is a cyclic charge and discharge curve of the hydrated lepidolite negative electrode material prepared in example 1 at a current density of 0.2A/g.
Fig. 5 is an XRD pattern of the hydrous lepidolite negative electrode material prepared in example 2.
FIG. 6 is a cyclic charge and discharge curve of the hydrated lepidolite negative electrode material prepared in example 2 at a current density of 0.2A/g.
Detailed Description
In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following description is further provided with reference to the specific embodiments and the accompanying drawings.
The potassium extraction rate is as follows: the lithium ion exchange rate refers to the exchange ratio of lithium ions to potassium ions in the reaction process, and the larger the exchange ratio of lithium ions to potassium ions is, the higher the potassium extraction rate is.
XRD pattern d(001)The change of the potassium extraction rate can reflect whether the lithium ions are replaced between the biotite layers, and the potassium extraction rate I can quantitatively calculate the exchange degree of the lithium ions and the potassium ions, and the formula is as follows:
wherein, I(001)*Is newly generated d in XRD pattern(001)*Intensity of diffraction Peak, I(001)Is original position d (in XRD pattern)001) Intensity of diffraction peak.
Example 1
The method for preparing the negative electrode material by modifying the biotite through the lithium ion exchange method comprises the following steps:
1) grinding biotite ore by a ball mill, and sieving by a 200-mesh sieve;
2) uniformly mixing the biotite ore powder obtained in the step 1) with 0.77mol/L lithium nitrate aqueous solution, wherein the mass volume ratio of the biotite ore powder to the lithium nitrate aqueous solution is 1 g: 250ml, adjusting the pH value of the mixed solution to 1.5 by using a dilute hydrochloric acid solution with the molar concentration of 0.5mol/L, then placing the mixed solution in a constant-temperature water bath kettle at 80 ℃ for stirring, filtering the mixed solution after 5 hours of reaction, collecting solid insoluble substances and drying to obtain the hydrated lepidolite negative electrode material.
Fig. 1 and 3 are XRD patterns of biotite raw ore and the hydrated lepidolite negative electrode material prepared in this example, respectively. As can be seen from fig. 1, the characteristic peak of biotite is very sharp and no other impurity peak exists, indicating that the crystallinity is good and no other mineral impurities exist; as can be seen from FIG. 3, the obtained product has high diffraction peak intensity, good crystallinity and single phase, and the X-ray diffraction peak spectrum of the biotite raw ore is compared to that of the biotite raw ore shows that: the structural crystal form of the electrolyte after ion exchange is not changed, and the potassium extraction rate is 89.7 percent.
The electrochemical performance was tested: adding 3% of polytetrafluoroethylene binder and acetylene black into the prepared hydrated lepidolite negative electrode material, wherein the mass ratio of finished hydrated lepidolite, acetylene black to polytetrafluoroethylene is 8: 1: 1, placing the mixture in an agate mortar for fully grinding, pressing into a thin sheet, and cutting according to needs for performance test.
Fig. 2 and 4 are the charge and discharge curves of the biotite raw ore and the hydrated lepidolite prepared in this example at a current density of 0.2A/g, respectively. Through calculation, the first discharge specific capacity of the biotite raw ore under the current density of 0.2A/g is 5.83F/g; the first specific discharge capacity of the hydrated lepidolite prepared in the embodiment is 8.89F/g under the current density of 0.2A/g, and is increased to a certain extent compared with 5.83F/g of biotite raw ore, so that the electrochemical performance of the modified hydrated lepidolite is obviously superior to that of the biotite raw ore.
Example 2
The method for preparing the negative electrode material by modifying the biotite through the lithium ion exchange method comprises the following steps:
1) grinding biotite ore by a ball mill, and sieving by a 200-mesh sieve;
2) uniformly mixing the biotite ore powder obtained in the step 1) with 0.77mol/L lithium nitrate aqueous solution, wherein the mass volume ratio of the biotite ore powder to the lithium nitrate aqueous solution is 1 g: 250ml, adjusting the pH value of the mixed solution to 1.5 by using a dilute hydrochloric acid solution with the molar concentration of 0.5mol/L, then placing the mixed solution in a constant-temperature water bath kettle at 80 ℃ for stirring, filtering the mixed solution after 10 hours of reaction, collecting solid insoluble substances and drying to obtain the hydrated lepidolite negative electrode material.
Fig. 5 is an X-ray diffraction pattern (XRD) of the hydrous lepidolite negative electrode material prepared in this example. As can be seen in the figure, the obtained product has high diffraction peak intensity, good crystallinity and single phase, and compared with the X-ray diffraction peak spectrum of the biotite raw ore, the X-ray diffraction peak spectrum of the biotite raw ore can be known as follows: the structural crystal form of the electrolyte after ion exchange is not changed, and the potassium extraction rate is 94.2 percent.
The electrochemical performance was tested: adding 3% of polytetrafluoroethylene binder and acetylene black into the prepared hydrated lepidolite, wherein the mass ratio of the finished hydrated lepidolite, the acetylene black to the polytetrafluoroethylene is 8: 1: 1, placing the mixture in an agate mortar for fully grinding, pressing into a thin sheet, and cutting according to needs for performance test.
Fig. 6 is a cyclic charge-discharge curve of the hydrated lepidolite prepared in the embodiment at a current density of 0.2A/g, and through calculation, the first specific discharge capacity of the hydrated lepidolite after 10 hours of reaction at the current density of 0.2A/g is 11.68F/g, which is greatly increased compared with 5.83F/g of biotite raw ore, which indicates that the electrochemical performance of the modified hydrated lepidolite is obviously superior to that of the biotite raw ore.
It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. Such variations and modifications as would be obvious to one skilled in the art are intended to be included within the scope of the present invention without departing from the spirit and scope thereof.

Claims (9)

1. The method for preparing the negative electrode material by modifying the biotite through the lithium ion exchange method is characterized in that the negative electrode material is hydrated lepidolite and is prepared by replacing potassium ions in the biotite with lithium ions.
2. The method according to claim 1, characterized in that it comprises in particular the steps of:
1) pulverizing biotite ore and sieving;
2) mixing the biotite obtained in the step 1) with an aqueous solution of a soluble lithium salt, adding an acid solution to adjust the mixed solution to be acidic, heating for reaction, filtering and drying to obtain the hydrated lepidolite negative electrode material.
3. The method as claimed in claim 2, wherein the biotite ore is crushed in step 1) and then passed through a 200-mesh screen.
4. The method as claimed in claim 2, wherein the pH of the mixed solution is adjusted to 1.3-1.5 by adding an acid solution before the reaction in step 2).
5. The method of claim 2, wherein in the step 2), the concentration of the soluble lithium salt aqueous solution is 0.77-0.80 mol/L; the mass volume ratio of the biotite to the soluble lithium salt aqueous solution is 1 g: 245-250 ml.
6. The method of claim 2, wherein in step 2), the soluble lithium salt is lithium nitrate.
7. The method as claimed in claim 2, wherein in the step 2), the acid solution is diluted hydrochloric acid with a concentration of 0.4-0.6 mol/L.
8. The method as claimed in claim 2, wherein the heating reaction conditions in step 2) are as follows: the temperature is 70-80 ℃, and the reaction time is 5-10 h.
9. The method of claim 8, wherein the heating reaction conditions are: the reaction temperature is 80 ℃, and the reaction time is 8-10 h.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1508194A (en) * 2002-12-17 2004-06-30 ϣ���ٹɷݹ�˾ Laminar silicate intercalation compound with increased expanding volume, its preparing method and use
CN103579601A (en) * 2012-07-18 2014-02-12 国立大学法人信州大学 Method for producing anode active material, and anode active material
CN106276983A (en) * 2016-07-22 2017-01-04 中国科学院青海盐湖研究所 A kind of preparation method of water solublity potassium salt
CN108329721A (en) * 2018-02-07 2018-07-27 南京工业大学 It is a kind of modified micaceous and its preparation method and application
CN109456621A (en) * 2017-09-06 2019-03-12 中南大学 Organic modified sheet silicate and preparation method thereof
CN109504857A (en) * 2018-11-30 2019-03-22 武汉工程大学 The method that magnesium ion exchange process extracts soluble potassium ion from biotite
CN109574018A (en) * 2018-12-11 2019-04-05 佛山欧神诺陶瓷有限公司 A kind of mesoporous nano material and preparation method thereof with humidity conditioning function

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1508194A (en) * 2002-12-17 2004-06-30 ϣ���ٹɷݹ�˾ Laminar silicate intercalation compound with increased expanding volume, its preparing method and use
CN103579601A (en) * 2012-07-18 2014-02-12 国立大学法人信州大学 Method for producing anode active material, and anode active material
CN106276983A (en) * 2016-07-22 2017-01-04 中国科学院青海盐湖研究所 A kind of preparation method of water solublity potassium salt
CN109456621A (en) * 2017-09-06 2019-03-12 中南大学 Organic modified sheet silicate and preparation method thereof
CN108329721A (en) * 2018-02-07 2018-07-27 南京工业大学 It is a kind of modified micaceous and its preparation method and application
CN109504857A (en) * 2018-11-30 2019-03-22 武汉工程大学 The method that magnesium ion exchange process extracts soluble potassium ion from biotite
CN109574018A (en) * 2018-12-11 2019-04-05 佛山欧神诺陶瓷有限公司 A kind of mesoporous nano material and preparation method thereof with humidity conditioning function

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