CN110462890B - Electrode active material, negative electrode and battery comprising the same, and method for producing the battery - Google Patents

Electrode active material, negative electrode and battery comprising the same, and method for producing the battery Download PDF

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CN110462890B
CN110462890B CN201780089129.6A CN201780089129A CN110462890B CN 110462890 B CN110462890 B CN 110462890B CN 201780089129 A CN201780089129 A CN 201780089129A CN 110462890 B CN110462890 B CN 110462890B
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sodium
active material
electrode active
lithium ion
ion battery
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CN110462890A (en
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郝小罡
蒋蓉蓉
王蕾
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Robert Bosch GmbH
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/049—Processes for forming or storing electrodes in the battery container
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes

Abstract

The present invention relates to an electrode active material for lithium ion batteries comprising particulate porous silicon or silicon alloy and sodium ions, wherein the sodium ions are embedded in the particulate porous silicon or silicon alloy. The present invention also relates to a negative electrode comprising the electrode active material and a lithium ion battery comprising the negative electrode. The invention also relates to a method for preparing the lithium ion battery.

Description

Electrode active material, negative electrode and battery comprising the same, and method for producing the battery
Technical Field
The present invention relates to an electrode active material for lithium ion batteries comprising particulate porous silicon or silicon alloy and sodium ions, wherein the sodium ions are embedded in the particulate porous silicon or silicon alloy. The present invention also relates to a negative electrode comprising the electrode active material and a lithium ion battery comprising the negative electrode. The invention also relates to a method for preparing the lithium ion battery.
Background
Silicon due to its interaction with Li 4.4 Si has high theoretical specific capacity of 4200mAh/g, so the Si is a promising selective negative electrode material. However, there are two issues that are considered critical for implementing their applications. One is volume change during charge and discharge, which results in electrode material cracking and fragmentation, thus losing electrical contact between individual silicon particles and severe capacity reduction. The other is the nature of the surface layer when Si is in contact with the electrolyte, also known as the solid-electrolyte-interface (SEI).
Disclosure of Invention
The object of the present invention is to solve the following problems: volume change during charging and discharging, poor Li + Conductivity and poor electronic conductivity.
According to one aspect, the object may be achieved by an electrode active material for lithium ion batteries comprising particulate porous silicon or silicon alloy and sodium ions, wherein the sodium ions are intercalated in the particulate porous silicon or silicon alloy.
According to another aspect of the present invention, there is provided a negative electrode comprising the electrode active material according to the present invention.
According to another aspect of the present invention, there is provided a lithium ion battery comprising the anode according to the present invention.
According to another aspect, the object may be achieved by a method of preparing a lithium ion battery, the method comprising the steps of:
1) providing a positive active material together with one or more sodium source materials, and providing granular porous silicon or silicon alloy as a negative active material;
2) assembling the positive active material of 1) together with one or more sodium source materials, the negative active material of 1) and an electrolyte into a lithium ion battery;
3) and (3) carrying out a formation process on the lithium ion battery in the step 2).
Drawings
Various aspects of the invention are explained in more detail in accordance with the accompanying drawings, in which:
FIGS. 1 to 3 are schematic diagrams of the formation process of the method of the present invention;
fig. 4 shows the cycle performance of the lithium ion batteries of example 1(E1), example 2(E2), example 3(E3) and Comparative Example (CE).
Detailed Description
All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety for all purposes to the same extent as if fully set forth herein, unless otherwise indicated.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
When an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. If a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
According to one aspect, the present invention relates to an electrode active material for lithium ion batteries comprising particulate porous silicon or silicon alloy and sodium ions, wherein the sodium ions are intercalated in the particulate porous silicon or silicon alloy.
According to one embodiment of the electrode active material according to the present invention, sodium ions may be present in the form of a sodium-silicon alloy. As shown in fig. 3, the sodium ions are no longer extracted by the anode material at the end of the formation process and during subsequent cycles, but remain in the particulate porous silicon or silicon alloy to form a sodium-silicon alloy. Because the radius of the sodium ions is larger than the lithium ions, the sodium ions can act as pillars in the silicon structure during cycling, thereby reducing volume shrinkage during cycling and keeping the channels for lithiation/delithiation open. On the other hand, during the subsequent cycle, lithium ions may be extracted and inserted into the sodium source material in addition to the positive electrode active material, wherein the sodium ions of the sodium source material are partially replaced with lithium ions.
In accordance with another embodiment of the electrode active material according to the present invention, the content of sodium ions may be 0.1 to 5 wt%, preferably 0.5 to 2 wt%, more preferably 0.8 to 1.5 wt%, based on the weight of the electrode active material. Since sodium ions have a larger radius than lithium ions, only a small amount of sodium ions can be intercalated into the silicon structure.
In accordance with another embodiment of the electrode active material according to the present invention, the average diameter of the particulate porous silicon or silicon alloy may be 20nm to 20 μm, preferably 0.1 to 10 μm.
According to another embodiment of the electrode active material according to the present invention, the particulate porous silicon or silicon alloyThe BET specific surface area of (B) may be 5 to 500m 2 /g。
According to another embodiment of the electrode active material according to the present invention, the particulate porous silicon or silicon alloy may have a pore volume of 0.3 to 50.0cm 3 /g。
In accordance with another embodiment of the electrode active material according to the present invention, the average pore diameter of the particulate porous silicon or silicon alloy may be 0.2nm to 0.1 μm.
According to another aspect, the present invention relates to a negative electrode comprising the electrode active material according to the present invention.
According to yet another aspect, the invention relates to a lithium ion battery comprising the anode according to the invention.
According to another aspect, the present invention relates to a method of making a lithium ion battery, the method comprising the steps of:
1) providing a positive active material together with one or more sodium source materials, and providing granular porous silicon or silicon alloy as a negative active material;
2) assembling the positive active material of 1) together with one or more sodium source materials, the negative active material of 1) and an electrolyte into a lithium ion battery;
3) and (3) carrying out a formation process on the lithium ion battery in the step 2).
1) Providing a positive active material together with one or more sodium source materials, and providing granular porous silicon or silicon alloy as a negative active material
In step 1), a positive electrode active material may be provided along with one or more sodium source materials, and particulate porous silicon or silicon alloy may be provided as a negative electrode active material.
In accordance with one embodiment of the method according to the present invention, the sodium source material may be one or more selected from positive active materials that may be used in a sodium ion battery. In particular, the sodium source material may be one or more selected from the group consisting of:
-binary, ternary or quaternary oxides of sodium and one or more transition metals;
-sulfates of sodium and one or more transition metals;
-sodium ferrocyanide and ferrocyanide of sodium and one or more transition metals;
-phosphates of sodium and one or more transition metals;
sodium pyrophosphate and pyrophosphates of sodium and one or more transition metals;
-sodium fluorophosphate and fluorophosphate salts of sodium and one or more transition metals; and
-an organic sodium salt,
wherein the one or more transition metals may be selected from the group consisting of: titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc.
According to another embodiment of the method according to the invention, the sodium source material may be one or more selected from the group consisting of: sodium vanadium phosphate, sodium iron phosphate, sodium vanadium fluorophosphate, sodium iron fluorophosphate, and sodium ferrocyanide.
In accordance with another embodiment of the method according to the invention, the sodium source material may be dehydrated.
In accordance with another embodiment of the method according to the present invention, the weight ratio of the positive electrode active material to the sodium source material may be 12.6:1 to 9:1, preferably 11.6:1 to 10:1, more preferably 11.1:1 to 10.5: 1.
2) Assembled battery
In step 2), the positive electrode active material of step 1) may be combined with one or more sodium source materials, the negative electrode active material of step 1), a separator, and an electrolyte such as 1M LiPF in EC: DMC (molar ratio 1:1) 6 And assembling the lithium ion battery.
Specifically, the cathode active material of step 1) along with one or more sodium source materials may be mixed with carbon black, graphite, and a binder such as polyvinylidene fluoride (PVDF) in a solvent such as DMF, TMF, THF, or NMP, and coated on an aluminum foil, and dried. On the other hand, the negative active material of step 1) may be mixed with carbon black, graphite, and a binder such as sodium polyacrylate, and coated on a copper foil, and dried.
3) Formation process
In step 3), a formation process may be performed on the lithium ion battery of step 2).
According to another embodiment of the method according to the invention, the formation process can be carried out at a current density of from C/5 to C/100, preferably from C/10 to C/50, more preferably about C/20.
In accordance with another embodiment of the method according to the present invention, the lithium ion battery of step 2) may be charged to 3.7 to 4.0V, preferably 3.8 to 3.9V, more preferably about 3.85V, maintained for 1 to 10 hours, preferably 4 to 6 hours, and then further charged to a charge cut-off voltage during the formation.
According to another embodiment of the method according to the invention, the formation process may be carried out up to a charge cut-off voltage of 4.15 to 4.25V, preferably about 4.2V, and up to a discharge cut-off voltage of 2.4 to 2.6V, preferably about 2.5V.
According to another embodiment of the method according to the invention, the formation process may be carried out up to a charge cut-off voltage of 4.3 to 4.4V, preferably about 4.35V, and up to a discharge cut-off voltage of 2.9 to 3.1V, preferably about 3.0V.
In accordance with another embodiment of the method according to the invention, during the formation sodium ions can be extracted from the positive electrode into the electrolyte (see fig. 1) and from the electrolyte into the negative electrode (see fig. 2).
In accordance with another embodiment of the method according to the present invention, during the formation, sodium ions may be intercalated into the particulate porous silicon or silicon alloy of the negative active material to form a sodium-silicon alloy. As shown in fig. 3, the sodium ions are no longer extracted by the anode material at the end of the formation process and during subsequent cycles, but remain in the particulate porous silicon or silicon alloy to form a sodium-silicon alloy. Because the radius of the sodium ions is larger than the lithium ions, the sodium ions can act as pillars in the silicon structure during cycling, thereby reducing volume shrinkage during cycling and keeping the channels for lithiation/delithiation open. On the other hand, during the subsequent cycle, lithium ions may be extracted and inserted into the sodium source material in addition to the positive electrode active material, wherein the sodium ions of the sodium source material are partially replaced with lithium ions.
4) Replacement with fresh electrolyte
According to another embodiment of the process according to the invention, the process may optionally also comprise a step 4) after step 3), in which step 4) the electrolyte may be replaced with a fresh electrolyte of the same composition, for example 1M LiPF in EC: DMC (molar ratio 1:1) 6 The replacement is performed so that the electrolyte in the battery contains substantially no more sodium ions, as shown in fig. 3.
According to the invention, sodium can be used to activate the silicon negative electrode. The sodium source material can be initially introduced into the positive electrode. During the initial formation cycle, sodium ions can be extracted from the positive electrode structure and diffuse from the positive electrode side to the negative electrode side. Thus, lithium and sodium ions in the electrolyte can be intercalated into the silicon negative electrode.
Since the radius of the sodium ions is larger than that of the lithium ions, the sodium ions can function as pillars in the silicon structure, thereby reducing volume change during charge and discharge. Thus, better cycle performance and better rate performance can be achieved.
In particular, the following problems can be solved by the present invention:
1) volume change during charge and discharge:
when some sodium ions are inserted into the silicon structure, the volume of the silicon structure expands but does not contract, and thus the volume change can be reduced;
2) poor Li + Conductivity:
since some sodium ions are inserted into the silicon structure, the diffusion path of lithium ions can be enlarged, thereby improving Li + Conductivity;
3) poor electronic conductivity:
the continuous volume change results in a loss of electrical contact between the silicon particles, however, according to the present invention, the volume change can be reduced and better electronic conductivity can be achieved.
Example 1 (E1):
preparing a positive electrode:
using Na 4 Fe(CN) 6 ·xH 2 O as sodium source material and dehydrated overnight to obtain Na 4 Fe(CN) 6 . Na was then added at a rate of 200rpm using a ball mill 4 Fe(CN) 6 Was mixed with conductive carbon black Super P (commercially available from Timcal) at a weight ratio of 8:2 for 2 hours to obtain a preliminary mixture.
10 grams of the preliminary mixture, 86.5 grams of NCM111 (commercially available from BASF), 2 grams of PVDF (commercially available from Solef), 1 gram of conductive carbon black Super P (commercially available from Timcal), and 0.5 gram of flake graphite (commercially available from Timcal) were weighed out and dry blended to obtain an intermediate mixture.
The intermediate mixture was added to an NMP solvent to obtain a cathode slurry, in which the solid content of the cathode slurry was adjusted to about 68 wt%. The positive electrode slurry was coated on an aluminum foil and dried at about 80 ℃, thereby obtaining a positive electrode.
Preparing a negative electrode:
the negative electrode composition was prepared using 40 wt% particulate porous silicon alloy (commercially available from 3M), 40 wt% graphite (commercially available from BTR), 10 wt% sodium polyacrylate (NaPAA), 8 wt% flake graphite (commercially available from Timcal), and 2 wt% conductive carbon black Super P (commercially available from Timcal). The negative electrode composition was coated on a copper foil and dried to obtain a negative electrode.
Assembling the battery:
using 1M LiPF in dimethyl carbonate (DMC) and Ethylene Carbonate (EC) (molar ratio 1:1) 6 As an electrolyte. A PI film (commercially available from DuPont) was used as the separator.
The positive electrode, negative electrode, electrolyte and separator were assembled into a pouch cell in an argon-filled glove box (MB-10compact, MBraun).
Formation process and subsequent cycle process:
electrochemical performance was evaluated on a LAND-CT 2001A battery test system (Wuhan, China) at room temperature.
The pouch cell was subjected to a formation process in which the pouch cell was charged to 3.85V at a current density of C/20, held for 5 hours, further charged to 4.2V, and discharged to 2.5V. The pouch cells were charged to 4.2V and discharged to 2.5V during subsequent cycles at a current density of 0.5C.
Fig. 4 shows the cycle performance of the lithium ion battery of example 1 (E1).
Example 2 (E2):
example 2(E2) was performed similarly to example 1, except that the pouch cells were charged and discharged at a current density of 0.1C every 50 cycles during the subsequent cycles, and at a current density of 0.5C for the other cycles.
Fig. 4 shows the cycle performance of the lithium ion battery of example 2 (E2).
Example 3 (E3):
example 3(E3) was performed similarly to example 1, except that the pouch cell was charged to 3.85V at a current density of C/20 during formation, held for 5 hours, further charged to 4.35V, and discharged to 3V; and during subsequent cycles the pouch cell was charged to 4.35V and discharged to 3V at a current density of 0.1C per 50 cycles and 0.5C for the other cycles.
Fig. 4 shows the cycle performance of the lithium ion battery of example 3 (E3).
Comparative Example (CE):
comparative Example (CE) was performed similarly to example 1, except that the positive electrode was prepared without using a sodium source material.
Fig. 4 shows the cycle performance of the lithium ion battery of Comparative Example (CE).
Potential applications for electrode active materials according to the present invention include, but are not limited to, lithium ion batteries with high energy densities that are acceptable for energy storage applications such as power tools, photovoltaic cells, and electric vehicles.
While certain embodiments have been described, these embodiments have been presented by way of example only, and should not be taken as limiting the scope of the invention. The appended claims and their equivalents should be construed to cover all such modifications, substitutions and alterations as fall within the true scope and spirit of the invention.

Claims (33)

1. A method of making a lithium ion battery, the method comprising the steps of:
1) providing a positive active material together with one or more sodium source materials, and providing granular porous silicon or a silicon alloy as a negative active material;
2) assembling the positive active material of 1) together with one or more sodium source materials, the negative active material of 1) and an electrolyte into a lithium ion battery;
3) and (3) carrying out a formation process on the lithium ion battery in the step 2).
2. The method of claim 1, wherein the sodium source material is one or more selected from the group consisting of:
-binary, ternary or quaternary oxides of sodium and one or more transition metals;
-sulfates of sodium and one or more transition metals;
-sodium ferrocyanide and ferrocyanide of sodium and one or more transition metals;
-phosphates of sodium and one or more transition metals;
sodium pyrophosphate and pyrophosphates of sodium and one or more transition metals;
-sodium fluorophosphate and fluorophosphate salts of sodium and one or more transition metals; and
-organic sodium salts.
3. The method of claim 2, wherein the one or more transition metals are selected from the group consisting of: titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc.
4. The method according to any one of claims 1 to 3, wherein the sodium source material is one or more selected from the group consisting of: sodium vanadium phosphate, sodium iron phosphate, sodium vanadium fluorophosphate, sodium iron fluorophosphate, and sodium ferrocyanide.
5. The method of any one of claims 1 to 3, wherein the sodium source material is dehydrated.
6. The method according to any one of claims 1 to 3, wherein the weight ratio of the positive electrode active material to the sodium source material is from 12.6:1 to 9: 1.
7. The method according to any one of claims 1 to 3, wherein the weight ratio of the positive electrode active material to the sodium source material is 11.6:1 to 10: 1.
8. The method of any one of claims 1 to 3, wherein the weight ratio of the positive electrode active material to the sodium source material is from 11.1:1 to 10.5: 1.
9. The method according to one of claims 1 to 3, characterized in that the formation process is carried out with a current density of C/5 to C/100.
10. The method according to one of claims 1 to 3, characterized in that the formation process is carried out at a current density of C/10 to C/50.
11. The method according to one of claims 1 to 3, characterized in that the formation process is carried out at a current density of about C/20.
12. The method according to one of claims 1 to 3, characterized in that in the formation process, the lithium ion battery of 2) is charged to 3.7 to 4.0V, held for 1 to 10 hours, and then further charged to a charge cut-off voltage.
13. The method according to one of claims 1 to 3, characterized in that in the formation process, the lithium ion battery of 2) is charged to 3.8 to 3.9V, held for 4 to 6 hours, and then further charged to a charge cut-off voltage.
14. The method of any one of claims 1 to 3, wherein during the formation, the lithium ion battery of 2) is charged to about 3.85V, held for 4 to 6 hours, and then further charged to a charge cut-off voltage.
15. Method according to one of claims 1 to 3, characterized in that the formation process is carried out up to a charge cut-off voltage of 4.15 to 4.25V and up to a discharge cut-off voltage of 2.4 to 2.6V.
16. The method according to one of claims 1 to 3, characterized in that the formation process is carried out up to a charge cut-off voltage of about 4.2V and up to a discharge cut-off voltage of about 2.5V.
17. Method according to one of claims 1 to 3, characterized in that the formation process is carried out up to a charge cut-off voltage of 4.3 to 4.4V and up to a discharge cut-off voltage of 2.9 to 3.1V.
18. The method according to one of claims 1 to 3, characterized in that the formation process is carried out up to a charge cut-off voltage of about 4.35V and up to a discharge cut-off voltage of about 3.0V.
19. The method according to any one of claims 1 to 3, wherein during the formation, sodium ions are extracted from the positive electrode into the electrolyte and are intercalated from the electrolyte into the negative electrode.
20. The method of claim 19, wherein during the forming, sodium ions are intercalated into the particulate porous silicon or silicon alloy of the negative active material to form a sodium-silicon alloy.
21. Method according to one of claims 1 to 3, characterized in that after step 3) the electrolyte is replaced with fresh electrolyte having the same composition.
22. Electrode active material for a lithium ion battery produced by the method according to one of claims 1 to 21, characterized in that the electrode active material comprises particulate porous silicon or silicon alloy and sodium ions, wherein the sodium ions are intercalated into the particulate porous silicon or silicon alloy.
23. The electrode active material of claim 22, wherein the sodium ions are present in the form of a sodium-silicon alloy.
24. The electrode active material according to claim 22 or 23, wherein the content of sodium ions is 0.1 to 5% by weight based on the weight of the electrode active material.
25. The electrode active material according to claim 22 or 23, wherein the content of sodium ions is 0.5 to 2% by weight based on the weight of the electrode active material.
26. The electrode active material according to claim 22 or 23, wherein the content of sodium ions is 0.8 to 1.5% by weight based on the weight of the electrode active material.
27. An electrode active material according to claim 22 or 23, wherein the average diameter of the particulate porous silicon or silicon alloy is from 20nm to 20 μm.
28. An electrode active material according to claim 22 or 23, wherein the average diameter of the particulate porous silicon or silicon alloy is 0.1 to 10 μm.
29. The electrode active material according to claim 22 or 23, wherein the particulate porous silicon or silicon alloy has a BET specific surface area of 5 to 500m 2 /g。
30. An electrode according to claim 22 or 23An active material, characterized in that the particulate porous silicon or silicon alloy has a pore volume of 0.3 to 50.0cm 3 /g。
31. An electrode active material according to claim 22 or 23, wherein the average pore size of the particulate porous silicon or silicon alloy is from 0.2nm to 0.1 μm.
32. Negative electrode for a lithium ion battery, characterized in that it comprises an electrode active material according to one of claims 22 to 31.
33. Lithium ion battery, characterized in that it comprises a negative electrode according to claim 32.
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