CN109935824B - Expanded graphite cathode material loaded with cross needle-shaped tin oxide and preparation method thereof - Google Patents

Expanded graphite cathode material loaded with cross needle-shaped tin oxide and preparation method thereof Download PDF

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CN109935824B
CN109935824B CN201711351875.6A CN201711351875A CN109935824B CN 109935824 B CN109935824 B CN 109935824B CN 201711351875 A CN201711351875 A CN 201711351875A CN 109935824 B CN109935824 B CN 109935824B
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expanded graphite
tin oxide
tin
directing agent
needle
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CN109935824A (en
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晏荦
汤占磊
仰韻霖
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Guangdong Kaijin New Energy Technology Co ltd
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    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses an expanded graphite cathode material loaded with cross needle-shaped tin oxide and a preparation method thereof. The preparation method comprises the steps of (1) dispersing expanded graphite, (2) preparing a mixed solution of tin salt and a structure directing agent, (3) dropwise adding the mixed solution of the tin salt and the structure directing agent, (4) refluxing, (5) reducing a sodium borohydride alkaline solution, (6) filtering and washing, and (7) calcining at a medium temperature, wherein the prepared expanded graphite cathode material of the tin oxide has a special morphological structure and excellent electrochemical performance.

Description

Expanded graphite cathode material loaded with cross needle-shaped tin oxide and preparation method thereof
Technical Field
The invention relates to the field of lithium battery cathode materials, in particular to an expanded graphite cathode material loaded with cross needle-shaped tin oxide and a preparation method of the material.
Background
With the frequent urgency of non-renewable energy sources such as coal, oil, natural gas and the like, the energy problem is a serious problem facing the 21 st century, and the development of new energy sources and renewable clean energy sources is very important. Compared with the traditional secondary battery, the lithium ion battery has the outstanding advantages of high working voltage, large specific energy, stable discharge voltage, long cycle life, no environmental pollution and the like, and is widely applied to small and light electronic devices such as mobile phones, notebook computers, portable measuring instruments and the like. And the power supply is also the preferred power supply for future hybrid electric vehicles and pure electric vehicles.
The cathode material is one of the key materials of the lithium ion battery, and the lithium ion battery cathode material which is commercially used at present is mainly a carbon cathode material. The lithium ion battery has the advantages of high specific capacity (200-400 mAh/g), low electrode potential (less than 1.0VvsLi +/Li), high cycle efficiency (more than 95%), long cycle life and the like. The carbon negative electrode material comprises mesocarbon microbeads (MCMB), graphite and amorphous carbon, wherein the graphite material has high theoretical lithium intercalation capacity, good conductivity and good layered structure, and is one of the important points of lithium battery research in recent years. The graphite material can be divided into artificial graphite and natural graphite, and the natural graphite has the advantages of large specific surface area, high specific capacity, high first efficiency and the like, but the solvent is easy to be co-inserted in the charging and discharging processes, so that the cycle performance of the graphite material is poor. Although artificial graphite has a low graphitization degree compared with natural graphite, it has advantages of good rate capability, good compatibility with an electrolyte solution, and good cycle stability, and thus has been a research hotspot in recent years.
However, due to the limitation of the prior art, the current artificial graphite cannot greatly improve the energy density of the lithium battery. In order to improve the energy density of the lithium battery, tin-based materials, silicon-based materials and transition metals have higher theoretical capacity, and thus are the mainstream of research on negative electrode materials. However, these materials have significant volume expansion and contraction changes during lithium intercalation/deintercalation, and the internal stress of the materials is large, so that the materials are easy to crack after repeated charge and discharge, fall off from a current collector, and the content of active substances is reduced, thereby causing the cycle performance of the materials to be poor. A novel efficient and stable electrode material is searched, and the technical problem which is continuously solved in the field of the current lithium battery cathode material is solved.
Disclosure of Invention
The purpose of the invention is: the invention provides a novel lithium battery cathode material and a preparation method thereof, and the novel lithium battery cathode material has a special shape, namely, tin oxide loaded on the surface of expanded graphite has a cross needle-shaped structure.
In order to achieve the purpose, the invention adopts the following technical scheme.
An expanded graphite cathode material loaded with cross needle-shaped tin oxide is characterized in that: the tin oxide is distributed on the surface of the expanded graphite in a cross needle shape.
As an improved technical scheme, the theoretical mass ratio of the tin oxide to the expanded graphite is 1: 20-1: 5.
As an improved technical scheme of the invention, the density of the negative electrode material is 0.164-0.518 g/cm3The specific surface area is 100 to 230m2/g。
The invention also provides a preparation method of the expanded graphite cathode material loaded with the cross needle-shaped tin oxide, which comprises the following steps:
s1, immersing the expanded graphite into water, and stirring for 10 min-2 h to obtain an expanded graphite suspension;
s2, preparing a tin-containing salt solution, and then adding a structure directing agent into the tin-containing salt solution for dissolving;
s3, slowly dripping the stanniferous salt solution containing the structure directing agent into the expanded graphite suspension;
s4, heating and refluxing the expanded graphite suspension treated in the step S3 for 0.5-2 h, and cooling to room temperature;
s5, dropwise adding an excessive sodium borohydride alkaline solution into the suspension treated in the step S4, and stirring for 2-5 hours to obtain a composite material containing tin oxide and expanded graphite;
s6, filtering and washing the composite material containing the tin oxide and the expanded graphite prepared in the step S5 until the pH value of the filtrate is neutral;
and S7, heating the composite material containing the tin oxide and the expanded graphite treated in the step S6 to 300-500 ℃ under the protection of inert gas, and preserving the heat for 1-3 hours to obtain the expanded graphite cathode material loaded with the cross needle-shaped tin oxide.
As an improved technical scheme of the invention, the structure directing agent is ionic polyelectrolyte.
As an improved technical scheme of the invention, the structure directing agent is polyvinylidene dimethyl ammonium chloride, polystyrene potassium sulfonate or polystyrene sodium sulfonate.
As an improved technical scheme of the invention, the mass concentration of the expanded graphite is 5-20 g/L.
As an improved technical scheme of the invention, the concentration of the tin-containing salt solution is 0.1-1 mol/L, and the mass ratio of the structure directing agent to Sn is 5-20: 1.
As a modified technical scheme, the use amount of the sodium borohydride alkaline solution is as follows: the molar ratio of sodium borohydride to Sn is more than or equal to 0.25: 1; the molar ratio of the alkali metal hydroxide to Sn is 2-4: 1.
As an improved technical scheme, in the finally prepared negative electrode material, the theoretical mass ratio of the tin oxide to the expanded graphite is 1: 20-1: 5.
Has the advantages that:
compared with the prior art, the lithium battery cathode material provided by the invention has a special shape structure, and has the advantages of high energy density, good charge-discharge cycle performance and the like. The reason was analyzed as follows:
1. the expanded graphite has rich pore structure, strong adsorbability, good conductivity and low resistivity, and presents new performance which is not possessed by the original graphite and intercalation materials due to the interaction of the insert and the graphite layer. Expanded graphite has better thermal and electrical conductivity than general graphite. In the expanded graphite material, some metals are selectively doped, the microstructure and the electronic state of graphite are changed, the conductivity of the graphite material is enhanced, electrons are more uniformly distributed on the surface of graphite particles, and polarization is reduced, so that the high-current charge and discharge performance of the graphite material is improved.
2. A structure-directing agent is added into the tin-containing salt solution, so that tin ions can be better combined with the expanded graphite sheet layer when acting with the expanded graphite, and the agglomeration of the tin ions in the expanded graphite sheet layer is prevented; during medium-temperature calcination, the tin oxide crystals can be guided to grow orderly on the surface of the expanded graphite.
3. The tin oxide has higher theoretical capacity in the negative electrode material of the lithium battery, when the tin oxide is firmly attached to the surface of the expanded graphite in a special shape, the expanded graphite buffers the volume shrinkage change of the tin oxide material in the lithium embedding/lithium removing process, so that the negative electrode material consisting of the tin oxide and the expanded graphite cannot crack and is not easy to fall off from a current collector after repeated charging and discharging, and the charging and discharging cycle performance of the negative electrode material is obviously improved. The tin oxide guided by the guiding agent is not received, and the tin oxide/expanded graphite material is agglomerated on the surface of the expanded graphite and is not firmly attached, so that the prepared tin oxide/expanded graphite material is used as a lithium battery cathode, the initial capacity is high, and the electrochemical performance is obviously reduced after repeated charge and discharge.
4. The mass ratio of the tin oxide to the expanded graphite is too low, the volume energy density of the expanded graphite is not improved much, and the mass ratio of the tin oxide to the expanded graphite is too high, so that the tin oxide is not firmly attached to the surface of the expanded graphite, and the electrochemical performance of the expanded graphite is remarkably reduced after the expanded graphite is charged and discharged for many times.
Drawings
Fig. 1 is an SEM image of the expanded graphite negative electrode material supporting cruciform needle-like tin oxide prepared in example 5;
FIG. 2 is an SEM image of the tin oxide/expanded graphite composite material prepared in example 9.
Detailed Description
So that those skilled in the art can clearly understand the invention, a detailed description of the invention will be given with reference to the detailed description and the accompanying drawings.
Example 1
S1: immersing expanded graphite into water, and stirring for 10min to obtain 5g/L expanded graphite turbid liquid;
s2: preparing 0.1mol/L tin-containing salt solution, and then adding a structure-directing agent polyvinylidene dimethyl ammonium chloride into the tin-containing salt solution for dissolving; the mass ratio of the addition amount of the structure directing agent to tin is 5: 1;
s3: slowly dripping 66.4mL of stanniferous salt solution containing the structure directing agent into 1L of expanded graphite turbid liquid within 1 min;
s4: heating and refluxing the expanded graphite suspension treated by the S3 for 0.5h, and cooling to room temperature;
s5: dissolving 62.7mg of sodium borohydride and 531.2mg of sodium hydroxide in 10mL of water, dropwise adding the solution into the suspension treated by S4, and stirring for 2 hours to prepare the composite material containing the tin oxide and the expanded graphite;
s6: filtering and washing the composite material containing the tin oxide and the expanded graphite prepared in the step S5 until the pH value of the filtrate is neutral;
s7: and heating the composite material containing the tin oxide and the expanded graphite treated by the S6 to 300 ℃ under the protection of inert gas, and preserving the heat for 3 hours to obtain the expanded graphite cathode material loaded with the cross needle-shaped tin oxide.
Example 2
S1: immersing expanded graphite into water, and stirring for 30min to obtain 10g/L expanded graphite suspension;
s2: preparing 0.3mol/L tin-containing salt solution, and then adding a structure-directing agent polyvinylidene dimethyl ammonium chloride into the tin-containing salt solution for dissolving; the mass ratio of the addition amount of the structure directing agent to tin is 10: 1;
s3: slowly dripping 22.1mL of stanniferous salt solution containing the structure directing agent into 1L of expanded graphite turbid liquid within 1 min;
s4: heating and refluxing the expanded graphite suspension treated by the S3 for 1h, and cooling to room temperature;
s5: dissolving 75.3mg of sodium borohydride and 796.8mg of sodium hydroxide in 10mL of water, dropwise adding the solution into the suspension treated by the S4, and stirring for 3 hours to prepare the composite material containing the tin oxide and the expanded graphite;
s6: filtering and washing the composite material containing the tin oxide and the expanded graphite prepared in the step S5 until the pH value of the filtrate is neutral;
s7: and heating the composite material containing the tin oxide and the expanded graphite treated by the S6 to 400 ℃ under the protection of inert gas, and preserving the heat for 2 hours to obtain the expanded graphite cathode material loaded with the cross needle-shaped tin oxide.
Example 3
S1: immersing expanded graphite into water, and stirring for 1h to obtain 15g/L expanded graphite turbid liquid;
s2: preparing 0.5mol/L tin-containing salt solution, and then adding a structure-directing agent polyvinylidene dimethyl ammonium chloride into the tin-containing salt solution for dissolving; the mass ratio of the addition amount of the structure directing agent to tin is 15: 1;
s3: slowly dripping 13.3mL of stanniferous salt solution containing the structure directing agent into 1L of expanded graphite turbid liquid within 30 s;
s4: heating and refluxing the expanded graphite suspension treated by the S3 for 1.5h, and cooling to room temperature;
s5: dissolving 75.3mg of sodium borohydride and 1062.4mg of sodium hydroxide in 10mL of water, dropwise adding the solution into the suspension treated by the S4, and stirring for 4 hours to prepare the composite material containing the tin oxide and the expanded graphite;
s6: filtering and washing the composite material containing the tin oxide and the expanded graphite prepared in the step S5 until the pH value of the filtrate is neutral;
s7: and heating the composite material containing the tin oxide and the expanded graphite treated by the S6 to 500 ℃ under the protection of inert gas, and preserving the heat for 1h to obtain the expanded graphite cathode material loaded with the cross needle-shaped tin oxide.
Example 4
S1: immersing expanded graphite into water, and stirring for 2 hours to obtain 20g/L expanded graphite turbid liquid;
s2: preparing 1mol/L tin-containing salt solution, and then adding a structure-directing agent polyvinylidene dimethyl ammonium chloride into the tin-containing salt solution for dissolving; the mass ratio of the addition amount of the structure directing agent to tin is 20: 1;
s3: slowly dripping 6.6mL of stanniferous salt solution containing the structure directing agent into 1L of expanded graphite turbid liquid within 30 s;
s4: heating and refluxing the expanded graphite suspension treated by the S3 for 2h, and cooling to room temperature;
s5: dissolving 62.7mg of sodium borohydride and 796.8mg of sodium hydroxide in 10mL of water, dropwise adding the solution into the suspension treated by the S4, and stirring for 5 hours to prepare the composite material containing the tin oxide and the expanded graphite;
s6: filtering and washing the composite material containing the tin oxide and the expanded graphite prepared in the step S5 until the pH value of the filtrate is neutral;
s7: and heating the composite material containing the tin oxide and the expanded graphite treated by the S6 to 400 ℃ under the protection of inert gas, and preserving the heat for 2 hours to obtain the expanded graphite cathode material loaded with the cross needle-shaped tin oxide.
Example 5
S1: immersing expanded graphite into water, and stirring for 2 hours to obtain 10g/L expanded graphite turbid liquid;
s2: preparing 0.5mol/L tin-containing salt solution, and then adding a structure-directing agent polyvinylidene dimethyl ammonium chloride into the tin-containing salt solution for dissolving; the mass ratio of the addition amount of the structure directing agent to tin is 10: 1;
s3: slowly dripping 13.3mL of stanniferous salt solution containing the structure directing agent into 1L of expanded graphite turbid liquid within 30 s;
s4: heating and refluxing the expanded graphite suspension treated by the S3 for 1h, and cooling to room temperature;
s5: dissolving 62.7mg of sodium borohydride and 796.8mg of sodium hydroxide in 10mL of water, dropwise adding the solution into the suspension treated by the S4, and stirring for 4 hours to prepare the composite material containing the tin oxide and the expanded graphite;
s6: filtering and washing the composite material containing the tin oxide and the expanded graphite prepared in the step S5 until the pH value of the filtrate is neutral;
s7: and heating the composite material containing the tin oxide and the expanded graphite treated by the S6 to 400 ℃ under the protection of inert gas, and preserving the heat for 2 hours to obtain the expanded graphite cathode material loaded with the cross needle-shaped tin oxide.
Example 6
S1: immersing expanded graphite into water, and stirring for 2 hours to obtain 10g/L expanded graphite turbid liquid;
s2: preparing 0.5mol/L tin-containing salt solution, and then adding a structure-directing agent polyvinylidene dimethyl ammonium chloride into the tin-containing salt solution for dissolving; the mass ratio of the addition amount of the structure directing agent to tin is 10: 1;
s3: slowly dripping 33.2mL of stanniferous salt solution containing the structure directing agent into 1L of expanded graphite turbid liquid within 1 min;
s4: heating and refluxing the expanded graphite suspension treated by the S3 for 1h, and cooling to room temperature;
s5: dissolving 156.7mg of sodium borohydride and 1992mg of sodium hydroxide in 10mL of water, then dropwise adding the solution into the suspension treated by S4, and stirring for 4 hours to prepare the composite material containing the tin oxide and the expanded graphite;
s6: filtering and washing the composite material containing the tin oxide and the expanded graphite prepared in the step S5 until the pH value of the filtrate is neutral;
s7: and heating the composite material containing the tin oxide and the expanded graphite treated by the S6 to 400 ℃ under the protection of inert gas, and preserving the heat for 2 hours to obtain the expanded graphite cathode material loaded with the cross needle-shaped tin oxide.
Example 7
S1: immersing expanded graphite into water, and stirring for 2 hours to obtain 10g/L expanded graphite turbid liquid;
s2: preparing 0.5mol/L tin-containing salt solution, and then adding a structure-directing agent polyvinylidene dimethyl ammonium chloride into the tin-containing salt solution for dissolving; the mass ratio of the addition amount of the structure directing agent to tin is 10: 1;
s3: slowly dripping 5.3mL of stanniferous salt solution containing the structure directing agent into 1L of expanded graphite turbid liquid within 30 s;
s4: heating and refluxing the expanded graphite suspension treated by the S3 for 1h, and cooling to room temperature;
s5: dissolving 25.1mg of sodium borohydride and 318.7mg of sodium hydroxide in 10mL of water, dropwise adding the solution into the suspension treated by the S4, and stirring for 4 hours to prepare the composite material containing the tin oxide and the expanded graphite;
s6: filtering and washing the composite material containing the tin oxide and the expanded graphite prepared in the step S5 until the pH value of the filtrate is neutral;
s7: and heating the composite material containing the tin oxide and the expanded graphite treated by the S6 to 400 ℃ under the protection of inert gas, and preserving the heat for 2 hours to obtain the expanded graphite cathode material loaded with the cross needle-shaped tin oxide.
Example 8
S1: immersing expanded graphite into water, and stirring for 2 hours to obtain 10g/L expanded graphite turbid liquid;
s2: preparing 0.5mol/L stanniferous salt solution, and then adding a structure-directing agent of potassium polystyrene sulfonate into the stanniferous salt solution for dissolving; the mass ratio of the addition amount of the structure directing agent to tin is 10: 1;
s3: slowly dripping 13.3mL of stanniferous salt solution containing the structure directing agent into 1L of expanded graphite turbid liquid within 30 s;
s4: heating and refluxing the expanded graphite suspension treated by the S3 for 1h, and cooling to room temperature;
s5: dissolving 62.7mg of sodium borohydride and 796.8mg of sodium hydroxide in 10mL of water, dropwise adding the solution into the suspension treated by the S4, and stirring for 4 hours to prepare the composite material containing the tin oxide and the expanded graphite;
s6: filtering and washing the composite material containing the tin oxide and the expanded graphite prepared in the step S5 until the pH value of the filtrate is neutral;
s7: and heating the composite material containing the tin oxide and the expanded graphite treated by the S6 to 400 ℃ under the protection of inert gas, and preserving the heat for 2 hours to obtain the expanded graphite cathode material loaded with the cross needle-shaped tin oxide.
Example 9
S1: immersing expanded graphite into water, and stirring for 2 hours to obtain 10g/L expanded graphite turbid liquid;
s2: preparing 0.5mol/L tin-containing salt solution;
s3: slowly dripping 13.3mL of stanniferous salt solution into 1L of expanded graphite suspension, and finishing dripping within 30 s;
s4: heating and refluxing the expanded graphite suspension treated by the S3 for 1h, and cooling to room temperature;
s5: dissolving 62.7mg of sodium borohydride and 796.8mg of sodium hydroxide in 10mL of water, dropwise adding the solution into the suspension treated by the S4, and stirring for 4 hours to prepare the composite material containing the tin oxide and the expanded graphite;
s6: filtering and washing the composite material containing the tin oxide and the expanded graphite prepared in the step S5 until the pH value of the filtrate is neutral;
s7: and heating the composite material containing the tin oxide and the expanded graphite treated by the S6 to 400 ℃ under the protection of inert gas, and preserving the heat for 2 hours to obtain the tin oxide/expanded graphite composite material.
The expanded graphite anode materials loaded with the cross-shaped needle-shaped tin oxide prepared in examples 1 to 8 and the tin oxide/expanded graphite composite material prepared in example 9 were assembled into a pair of lithium half cells, and the electrochemical properties of each material were measured as follows:
TABLE 1 Density, initial Capacity and Capacity after 50 and 300 cycles of materials from examples 1-9
It is apparent that the above examples are only examples for clearly illustrating the present invention, and are not to be construed as limiting the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modifications made on the basis of the examples of the present invention, which are common knowledge, are within the scope of the present invention.

Claims (10)

1. An expanded graphite cathode material loaded with cross needle-shaped tin oxide is characterized in that: the tin oxide is distributed on the surface of the expanded graphite in a cross needle shape.
2. The anode material according to claim 1, characterized in that: the theoretical mass ratio of the tin oxide to the expanded graphite is 1: 20-1: 5.
3. The anode material according to claim 2, characterized in that: the density of the negative electrode material is 0.164-0.518 g/cm3The specific surface area is 100 to 230m2/g。
4. A preparation method of an expanded graphite cathode material loaded with cross needle-shaped tin oxide comprises the following steps:
s1, immersing the expanded graphite into water, and stirring for 10 min-2 h to obtain an expanded graphite suspension;
s2, preparing a tin-containing salt solution, and then adding a structure directing agent into the tin-containing salt solution for dissolving;
s3, slowly dripping the stanniferous salt solution containing the structure directing agent into the expanded graphite suspension;
s4, heating and refluxing the expanded graphite suspension treated in the step S3 for 0.5-2 h, and cooling to room temperature;
s5, dropwise adding an excessive sodium borohydride alkaline solution into the suspension treated in the step S4, and stirring for 2-5 hours to obtain a composite material containing tin oxide and expanded graphite;
s6, filtering and washing the composite material containing the tin oxide and the expanded graphite prepared in the S5 until the pH value of the washing liquid is neutral;
and S7, heating the composite material containing the tin oxide and the expanded graphite treated in the step S6 to 300-500 ℃ under the protection of inert gas, and preserving the heat for 1-3 hours to obtain the expanded graphite cathode material loaded with the cross needle-shaped tin oxide.
5. The method of claim 4, wherein: the structure-directing agent is an ionic polyelectrolyte.
6. The method of claim 5, wherein: the structure directing agent is polyvinylidene dimethyl ammonium chloride, polystyrene potassium sulfonate or polystyrene sodium sulfonate.
7. The method of claim 4, wherein: the mass concentration of the expanded graphite is 5-20 g/L.
8. The method of claim 4, wherein: the concentration of the tin-containing salt solution is 0.1-1 mol/L, and the mass ratio of the structure directing agent to Sn is 5-20: 1.
9. The method according to claim 4, wherein the alkaline solution of sodium borohydride is used in an amount of: the molar ratio of sodium borohydride to Sn is more than or equal to 0.25: 1; the molar ratio of the alkali metal hydroxide to Sn is 2-4: 1.
10. The method of claim 4, wherein: in the finally prepared negative electrode material, the theoretical mass ratio of the tin oxide to the expanded graphite is 1: 20-1: 5.
CN201711351875.6A 2017-12-15 2017-12-15 Expanded graphite cathode material loaded with cross needle-shaped tin oxide and preparation method thereof Active CN109935824B (en)

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