LITHIUM-ION BATTERY WITH SILICON-BASED COMPOSITE MATERIAL WITH THREE-DIMENSIONAL BINDING NETWORK AND METHOD FOR PRODUCING THE SAME

Abstract

Lithium-ion battery comprising a cathode, an electrolyte and an anode, wherein the initial surface capacitance a of the cathode and the initial surface capacitance b of the anode satisfy the formulas 1 < ( b ⋅ ( 1 − ε ) / a ) ≤ 1.2 preferably 1.05 ≤ (b ⋅ (1 − ε) / a) ≤ 1.15 preferred 1.08 ≤ ( b ⋅ ( 1 − ε ) / a ) ≤ 1.12 0 < ε ≤ ( ( a ⋅ η 1 ) / 0.6 − ( a − b ⋅ ( 1 − η 2 ) ) ) / b where ε the degree of prelithiation of the anode, η1 the initial Coulomb efficiency of the cathode, and η2 is the initial Coulomb efficiency of the anode, wherein the electrode material of the anode comprises a silicon-based composite material with a three-dimensional bonding network and improved interaction between binder and silicon-based material, wherein the silicon-based composite material is produced by a process comprising introducing silane coupling agent with amine and / or imine groups into a slurry containing silicon-based material, a carboxyl-containing binder, and conductive carbon, during stirring, wherein the amount of the silane coupling agent with amine and / or imine groups is 0.01 - 2.5 wt.%, based on the weight of the silicon-based material.

Description

Technical area

[0001] The present invention relates to a lithium-ion battery comprising a silicon-based composite material with a three-dimensional bonding network and improved interaction between the binder and the silicon-based material; as well as a method for producing the lithium-ion battery. State of the art

[0002] With the rapid development and popularization of portable electronic devices and electric vehicles, the need for lithium-ion batteries with increased energy and power density is becoming increasingly urgent. Silicon is a promising alternative electrode material for lithium-ion batteries due to its large theoretical capacity (Li 15 Si4, 3579 mAh g -1 ) and moderate operating voltage (0.4 V against Li / Li + ).

[0003] However, there are many challenges for the practical application of silicon. For example, during the lithiation / delithiation process, silicon undergoes dramatic expansion and contraction, causing numerous cracks in both the Si-based active materials and the electrode. These cracks lead to a loss of electronic conductivity. Furthermore, the cracks also lead to continuous growth of the solid electrolyte interphase (SEI), resulting in a loss of ionic conductivity and Li consumption, thus leading to rapid capacity degradation. Serious efforts have been made in designing Si-based materials with nanoscale or porous structures to mitigate the negative volume effect and improve the electrochemical properties.

[0004] In addition to the active materials, recent studies have shown that the binder network also plays a crucial role in maintaining electrode integrity during volume changes in the electrode and is related to many important electrochemical properties, especially cycling properties.

[0005] Among all types of binders, carboxyl-containing binders, such as polyacrylic acid (PAA), carboxymethylcellulose (CMC), and sodium alginate (SA), are more widely used because the carboxyl groups on the binders can form hydrogen bonds with silicon. However, the hydrogen bonds formed by carboxyl groups are not yet strong enough to withstand the large volume change of silicon, especially in situations of high mass loading. Furthermore, the bonding network formed by the above-mentioned linear binder is also not strong enough to maintain electrode integrity during long cycling. There is a need for further modification to improve the binder.

[0006] On the other hand, in the effort to design high-performance batteries, reducing the particle size of the active material to the nanoscale can help shorten the diffusion length of charge carriers, improve the diffusion coefficient of Li ions, and thus achieve faster reaction kinetics. However, nanoscale active materials have a large surface area, which leads to a high irreversible capacity loss due to the formation of a solid electrode interphase (SEI). In the silicon oxide-based anode, the irreversible reaction during the first lithiation also leads to a large irreversible capacity loss in the initial cycle. Due to this irreversible capacity loss, Li is consumed in the cathode, reducing the capacity of the full cell.

[0007] Even worse for the Si-based anode, repeated volume changes during cycling expose more and more fresh surface area on the anode, leading to continuous SEI growth. And because of the continuous SEI growth, Li in the cathode is continuously consumed, leading to capacity degradation for the full cell.

[0008] Additional or supplementary Li can be provided by prelithiation of the anode to provide more lithium ions to compensate for SEI or other lithium consumption during formation. When prelithiation of the anode is performed, the irreversible capacity loss can be compensated in advance without Li consumption from the cathode. This results in higher cell efficiency and capacity.

[0009] However, a degree of prelithiation to precisely compensate for the irreversible lithium loss from the anode does not contribute to solving the problem of lithium consumption from the cathode during cycling. Therefore, in this case, the cycling performance did not improve. To compensate for the lithium loss from the cathode during cycling, over-prelithiation is performed in the present invention.

[0010] DE 10 2013 218 078 A1 describes a regeneration process for lithium-ion batteries. US 2014 / 0 346 618 A1 discloses silicon-containing active materials for electrochemical cells. Summary of the invention

[0011] It is therefore an object of the present invention to provide a further modification of the binder used in a silicon-based composite material for lithium-ion batteries. According to the invention, a three-dimensional bonding network and improved interaction between the binder and the silicon-based material can be created in the silicon-based composite material by additionally incorporating a treatment material into the composite material, wherein the treatment material is a silane coupling agent with amine and / or imine groups.

[0012] According to the invention, an improved interaction between a binder and a silicon-based material can be achieved through covalent bonds formed between the hydrolyzable ends in the silane coupling agent and Si-OH. Furthermore, the silane coupling agent containing amine and / or imine groups is bonded to the binder via a covalent bond formed by the amine / imine group in the silane coupling agent and the carboxyl group contained in the binder.

[0013] The present invention provides a lithium-ion battery comprising a cathode, an electrolyte and an anode, wherein the initial surface capacity a of the cathode and the initial surface capacity b of the anode satisfy the formulas 1<(b⋅(1−ε) / a)≤1.2 preferably 1.05≤(b⋅(1−ε) / a)≤1.15 preferred 1.08≤(b⋅(1−ε) / a)≤1.12 0<ε≤((a⋅η1) / 0.6−(a−b⋅(1−η2))) / b where ε is the degree of prelithiation of the anode, η1 is the initial Coulomb efficiency of the cathode, and η2 is the initial Coulomb efficiency of the anode.

[0014] The electrode material of the anode contains a silicon-based composite material with a three-dimensional bonding network and improved interaction between the binder and the silicon-based material.

[0015] The silicon-based composite material is produced by a process comprising the steps of introducing a silane coupling agent containing amine and / or imine groups into a slurry containing silicon-based material, a carboxyl-containing binder, and conductive carbon while stirring. The amount of the silane coupling agent containing amine and / or imine groups is 0.01-2.5 wt%, based on the weight of the silicon-based material. Short description of the drawings Fig.1 is a schematic representation of a three-dimensional bonding network not according to the invention and the corresponding structural formula when polydopamine is added to the silicon-based composite material. Fig. Figure 2 is transmission electron microscope (TEM) images showing (a) raw Si particles, and Si@PD particles prepared in (b) Reference Example 1 and (c) Comparative Example 1b. Fig. Figure 3 is a schematic representation of the three-dimensional bonding network and the corresponding structural formula when silane coupling agent with amine and / or imine groups is added to the silicon-based composite material. Fig. Figure 4 is Fourier transform infrared (FT-IR) spectra of (a) the Si electrode prepared in Example 6 incorporating 1 wt% silane coupling agent KH550, (b) raw Si, and (c) PAA binder. Fig.5 is a graph showing the cycling property of the Si electrodes prepared in (a) Reference Example 1, (b) Comparative Examples 1a and (c) 1b at a low mass loading of active materials. Fig. Figure 6 is a graph showing the cycling property of the Si electrodes prepared in (a) Reference Example 2 and (b) Comparative Example 2 at a high mass loading of active materials. Fig. 7 is a graph showing the cycling characteristics of the Si electrode prepared in Comparative Example 1a and the modified Si electrodes prepared in Examples 3-6 and Comparative Example 3 at a low mass loading of active materials. Fig. Figure 8 is a graph showing the cycling property of the modified Si electrodes prepared in (a) Example 7 and (b) Comparative Example 2 at a high mass loading of active materials. Fig.9 is a graph showing the cycling characteristics of the Si electrodes prepared in Examples 4-6 and Comparative Example 4. Fig. Figure 10 shows the cycle characteristics of the full cells from example P1-E1. Fig. Figure 11 shows the normalized energy densities of the full cells from example P1-E1. Fig. Figure 12 shows the cycle characteristics of the full cells from example P1-E2. Fig. Figure 13 shows the normalized energy densities of the full cells from example P1-E2. Fig. Figure 14 shows the cycling properties of the full cells from example P1-E3 at prelithiation degrees ε of a) 0 and b) 22%. Fig. Figure 15 shows the discharge / charge curve of the cell of Comparative Example P2-CE1, where “1”, “4”, “50”, and “100” represent the 1st, 4th, 50th, and 100th cycles, respectively. Fig.Figure 16 shows the discharge / charge curve of the cell from example P2-E1, where “1”, “4”, “50”, and “100” represent the 1st, 4th, 50th, and 100th cycles, respectively. Fig. Figure 17 shows the cycling characteristics of the cells from a) comparative example P2-CE1 (dashed line) and b) example P2-E1 (solid line). Fig. Figure 18 shows the average charging voltage a) and the average discharging voltage b) of the cell from comparative example P2-CE1. Fig. Figure 19 shows the average charging voltage a) and the average discharging voltage b) of the cell from example P2-E1. Detailed description of the preferred embodiments

[0016] Unless otherwise indicated, all publications, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety as if fully set forth.

[0017] Unless otherwise defined, all technical and scientific terms used herein have the same meanings commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present description, including the definitions, governs.

[0018] When an amount, concentration, or other value or parameter is stated either as a range, preferred range, or a list of upper preferred values ​​and lower preferred values, it is to be understood as a specific disclosure of all ranges formed by combining any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether the ranges are expressly disclosed. When a range of numerical values ​​is stated herein, unless otherwise described, the range is intended to include its endpoints and all whole numbers and fractions within the range.

[0019] According to the invention, a three-dimensional bonding network can be created in the silicon-based composite material used in lithium-ion batteries by introducing a treatment material into the composite material, wherein the treatment material is a silane coupling agent having amine and / or imine groups.

[0020] In the present invention, the silicon-based material may take any suitable form of silicon-based material as long as its surface can bear a hydroxyl group. Examples include silicon particles, silicon films, and so on. For example, silicon nanoparticles are used in the examples of the present invention.

[0021] Within the scope of the present invention, the carboxyl-containing binder can be any suitable binder as long as it contains carboxyl groups. The preferred binder is selected from the group consisting of polyacrylic acid (hereinafter abbreviated as "PAA"), carboxymethylcellulose (hereinafter abbreviated as "CMC"), sodium alginate (hereinafter abbreviated as "SA"), copolymers thereof, and combinations thereof.

[0022] In the context of the present invention, the silane coupling agent having amine and / or imine groups may be any suitable silane coupling agent as long as it carries amine groups, or imine groups, or both amine and imine groups.

[0023] The abbreviated symbol “Si@PD” is used to denote the PD-coated Si-based material and can be clearly understood by those skilled in the art.

[0024] Fig.Figure 1 shows a schematic representation of the three-dimensional bonding network after PD is added to the silicon-based composite material. Fig.As can be seen in Figure 1, the silicon-based material consists of silicon nanoparticles covered with a SiO2 thin film generated by air oxidation. In the absence of PD coating, the interaction between silicon and the binder (herein, PAA) results from the hydrogen bonds formed by the carboxyl group in the binder and the Si-OH on the Si surface. In the presence of PD coating, the interaction is changed to hydrogen bonds formed by the catechol groups on PD and the Si-OH on the surface of the Si particles. These hydrogen bonds are stronger than the hydrogen bonds formed between the carboxyl group in PAA and the Si-OH on the Si particles. The imine groups of PD then react with the carboxyl groups of the binder, for example, PAA, through a condensation reaction, thus forming a three-dimensional bonding network.

[0025] A silicon-based composite material with a three-dimensional bonding network according to the invention comprises a silicon-based material, a polydopamine coating on the silicon-based material, a carboxyl-containing binder, and conductive carbon. The average thickness of the polydopamine coating layer on the silicon-based material can be in the range of 0.5 to 2.5 nm, preferably 1 to 2 nm. Within the above-mentioned range, the PD content corresponds to approximately 5-8 wt%, based on the weight of the Si-based material.

[0026] Fig. Figure 2 shows transmission electron microscope (TEM) images of raw Si particles and Si@PD particles. Fig. 2a, a SiO2 thin film (about 3 nm) is deposited on the surface of raw nano-Si. After PD coating, the thickness of the outer layer increases to about 5 nm, as shown in Fig.2b, which shows that the silicon particles are uniformly coated with a PD layer with a thickness of about 1 - 2 nm. Fig. 2c corresponds to Comparative Example 1b, where the thickness of a PD layer is about 3 nm.

[0027] The manufacturing method for the above-mentioned silicon-based composite material having a three-dimensional bonding network according to the invention comprises: (1) dispersing silicon-based material in a buffer solution containing dopamine; (2) initiating in situ polymerization of dopamine on the surface of the silicon-based material by air oxidation; (3) collecting the polydopamine-coated silicon-based material; and (4) crosslinking polydopamine to form a carboxyl-containing binder.

[0028] The present invention provides a silicon-based composite material with a three-dimensional bonding network, and the composite material is prepared by a process comprising introducing a silane coupling agent having amine and / or imine groups into a slurry containing a silicon-based material, a carboxyl-containing binder, and conductive carbon while stirring. The amount of the silane coupling agent is 0.01-2.5 wt%, preferably 0.05-2.0 wt%, more preferably 0.1-2.0 wt%, and more preferably 0.1-1.0%, based on the weight of the silicon-based material.

[0029] In one embodiment of the present invention, the examples of silane coupling agents having amine and / or imine groups may be suitable silane coupling agents carrying amine groups, or imine groups, or both amine and imine groups, and the preferred examples thereof are one or more selected from the group consisting of γ-aminopropylmethyldiethoxysilane (NH2C3H6CH3Si(OC2H5)2), γ-aminopropylmethyldimethoxysilane (NH2C3H6CH3Si(OCH3)2), γ-aminopropyltriethoxysilane (NH2C3H6Si(OC2H5)3), γ-aminopropyltrimethoxysilane (NH2C3H6Si(OCH3)3), N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (NH2C2H4NHC3H6Si(OCH3)3), N-(β-aminoethyl)-γ-aminopropyltriethoxysilane (NH2C2H4NHC3H6Si(OC2H5)3), N-(β-Aminoethyl)-γ-aminopropylmethyldimethoxysilane (NH2C2H4NHC3H6SiCH3(OCH3)2), N,N-(Aminopropyltriethoxy)silane (HN[(CH2)3Si(OC2H5)3]2), γ-Trimethoxysilylpropyldiethylenetriamine (NH2C2H4NHC2H4NHC3H6Si(OCH3)3), γ-Divinyltriamine-propylmethyldimethoxysilane (NH2C2H4NHC2H4NHC3H6CH3Si(OCH3)2),Bis-γ-trimethoxysilylpropylamine, aminonehexyltrimethoxysilane, and aminonehexylmethyldimethoxysilane.

[0030] Fig. Figure 3 is a schematic representation of the three-dimensional bonding network after a silane coupling agent containing amine and / or imine groups is added to the silicon-based composite. The exemplified silane coupling agent KH550 contains three hydrolyzable ends (-OC2H5) and one non-hydrolyzable end (-C3H6-NH2). During slurry preparation and further vacuum drying, the hydrolyzable ends of the silane coupling agent hydrolyze to form covalent bonds with Si-OH on the silicon surface or with hydrolyzable ends of another silane coupling agent; on the other hand, the -NH2 group in the silane coupling agent reacts with the -COOH group in the carboxyl-containing binder, thus forming a strong three-dimensional bonding network.

[0031] FT-IR spectra in Fig.4 shows evidence of the formation of the three-dimensional network connected by covalent bonds. The peak at 940 cm -1 in Si nanoparticles is attributable to the vibration of the silanol OH group on the surface of nano-Si. This peak almost disappears on the Si electrode. This is due to the condensation of silanol groups on the Si surface with hydrolyzable ends of KH550. The peak at 1713 cm -1 in PAA corresponding to the stretching vibration of C=O in carboxyl group is 1700 cm -1 in the Si electrode is blue-shifted due to the formation of amide. This result demonstrates the cross-linking reaction between the -COOH group in the PAA binder and the -NH2 group in KH550.

[0032] The manufacturing method for the above-mentioned silicon-based composite material having a three-dimensional bonding network comprises: introducing a silane coupling agent having amine and / or imine groups into a slurry containing silicon-based material, a carboxyl-containing binder, and conductive carbon while stirring.

[0033] Accordingly, the present invention provides a silicon-based composite material with a three-dimensional bonding network for lithium-ion batteries.

[0034] The present invention further relates to an electrode material containing the silicon-based composite material produced by the above-mentioned method.

[0035] The present invention further relates to a lithium-ion battery containing the silicon-based composite material produced by the above-mentioned method.

[0036] When the cathode efficiency is higher than the anode efficiency, prelithiation can generally effectively increase cell capacity by increasing the initial Coulombic efficiency. In this case, maximum energy density can be achieved. For a cell where lithium loss may occur during cycling, prelithiation can also improve cycling performance if over-prelithiation is performed. Over-prelithiation provides a reservoir of lithium throughout the electrochemical system, and the additional lithium in the anode compensates for the potential lithium consumption from the cathode during cycling.

[0037] The higher the degree of prelithiation, the better the cycling performance can generally be achieved. However, a higher degree of prelithiation is associated with a much larger anode. Due to the increased anode weight and volume, the cell energy density decreases. Therefore, the degree of prelithiation should be carefully controlled to balance cycling performance and energy density.

[0038] The present invention relates to a lithium-ion battery comprising a cathode, an electrolyte and an anode, wherein the anode contains the electrode material according to the invention, and wherein the initial surface capacity a of the cathode and the initial surface capacity b of the anode satisfy the formulas 1<(b⋅(1−ε) / a)≤1.2 where 0<ε≤((a⋅η1) / 0.6−(a−b⋅(1−η2))) / b ε is the degree of prelithiation of the anode, η1 is the initial Coulomb efficiency of the cathode, and η2 is the initial Coulomb efficiency of the anode.

[0039] In the context of the present invention, the term “surface capacity” refers to the specific surface capacity in mAh / cm 2 , the electrode capacity per unit surface area of ​​the electrode. The term "initial capacity of the cathode" refers to the initial delithiation capacity of the cathode, and the term "initial capacity of the anode" refers to the initial lithiation capacity of the anode.

[0040] According to the invention, the term "prelithiation degree" ε of the anode can be calculated as (b - a x) / b, where x is the balance of the anode capacity after prelithiation and the cathode capacity. For safety reasons, the anode capacity is usually set slightly larger than the cathode capacity, and the balance of the anode capacity after prelithiation and the cathode capacity can be selected from greater than 1 to 1.2, preferably from 1.05 to 1.15, more preferably from 1.08 to 1.12, and most preferably about 1.1.

[0041] According to one embodiment of the lithium-ion battery according to the invention, the initial surface capacity a of the cathode and the initial surface capacity b of the anode satisfy the formulas 1.05≤(b⋅(1−ε) / a)≤1.15 preferably 1.08≤(b⋅(1−ε) / a)≤1.12

[0042] According to a further embodiment of the lithium-ion battery according to the invention, the degree of prelithiation of the anode can be defined as ε=((a⋅η1) / c−(a−b⋅(1−η2))) / b 0.6≤c<1 preferably 0.7≤c<1 preferred 0.7≤c≤0.9 particularly preferred 0.75≤c≤0.85 where c is the depth of discharge (DoD) of the anode. In particular, ε = (b (1 - η2) - a (1 - η1)) / b when c = 1.

[0043] According to a further embodiment of the lithium-ion battery according to the invention, the anode active material can be selected from the group consisting of carbon, silicon, intermetallic compound of silicon, silicon oxide, silicon alloy and mixtures thereof.

[0044] According to a further embodiment of the lithium-ion battery according to the invention, the cathode active material can be selected from the group consisting of lithium nickel oxide, lithium cobalt oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium nickel cobalt manganese oxide, and mixtures thereof.

[0045] According to a further aspect, the present invention relates to a method for producing a lithium-ion battery comprising a cathode, an electrolyte and an anode, wherein the anode contains the electrode material according to the invention, and wherein the method comprises the following steps: 1) Prelithiation of the anode active material or the anode up to a degree of prelithiation ε, and 2) Assembling the anode and the cathode to obtain the lithium-ion battery, characterized in that the initial surface capacity a of the cathode, the initial surface capacity b of the anode and the degree of prelithiation ε satisfy the formulas 1<(b⋅(1−ε) / a)≤1.2 0<ε≤((a⋅η1) / 0.6−(a−b⋅(1−η2))) / b where ε is the degree of prelithiation of the anode, η1 is the initial Coulomb efficiency of the cathode, and η2 is the initial Coulomb efficiency of the anode.

[0046] In the context of the present invention, the term “surface capacity” refers to the specific surface capacity in mAh / cm 2 , the electrode capacitance per unit surface area of ​​the electrode. The term "initial cathode capacitance" refers to the initial delithiation capacity of the cathode, and the term "initial anode capacitance" refers to the initial lithiation capacity of the anode.

[0047] According to the invention, the term "prelithiation degree" ε of the anode can be calculated as (b - a x) / b, where x is the balance of the anode capacity after prelithiation and the cathode capacity. For safety reasons, the anode capacity is usually set slightly larger than the cathode capacity, and the balance of the anode capacity after prelithiation and the cathode capacity can be selected from greater than 1 to 1.2, preferably from 1.05 to 1.15, more preferably from 1.08 to 1.12, and particularly preferably about 1.1.

[0048] The prelithiation process is not particularly limited. For example, lithiation of the anode active material substrate can be carried out in various ways. A physical process includes deposition of a lithium coating layer on the surface of the anode active material substrate, for example, silicon particles, thermally induced diffusion of lithium into the substrate, for example, silicon particles, or spraying stabilized Li powder onto the anode strip. An electrochemical process includes using silicon particles and a lithium metal plate as the electrodes, and applying an electrochemical potential to intercalate Li. + -ions into the bulk of the silicon particles. An alternative electrochemical process involves assembling a half-cell with silicon particles and Li-metal foil electrodes, charging the half-cell, and disassembling the half-cell to obtain lithiated silicon particles.

[0049] According to one embodiment of the process according to the invention, the initial surface capacity a of the cathode and the initial surface capacity b of the anode satisfy the formulas 1.05≤(b⋅(1−ε) / a)≤1.15 preferably 1.08≤(b⋅(1−ε) / a)≤1.12

[0050] According to a further embodiment of the process according to the invention, the degree of prelithiation of the anode can be defined as ε=((a⋅η1) / c−(a−b⋅(1−η2))) / b 0.6≤c<1 preferably 0.7≤c<1 preferred 0.7≤c≤0.9 particularly preferred 0.75≤c≤0.85 where c is the depth of discharge (DoD) of the anode. In particular, ε = (b (1 - η2) - a (1 - η1)) / b when c = 1.

[0051] According to a further embodiment of the method according to the invention, the anode active material can be selected from the group consisting of carbon, silicon, intermetallic compound of silicon, silicon oxide, silicon alloy and mixtures thereof.

[0052] According to a further embodiment of the process according to the invention, the cathode active material can be selected from the group consisting of lithium nickel oxide, lithium cobalt oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium nickel cobalt manganese oxide, and mixtures thereof.

[0053] State-of-the-art prelithiation processes often involve a treatment of coated anode strip, which may be an electrochemical process or physical contact of the anode with stabilized lithium metal powder.

[0054] However, these prelithiation processes require additional steps to the existing battery manufacturing process. Furthermore, due to the highly active nature of the prelithiated anode, the subsequent battery manufacturing process requires a well-controlled humidity environment, resulting in increased cell manufacturing complexity.

[0055] The present invention provides an alternative method for in-situ prelithiation. The lithium source for prelithiation originates from the cathode. During the first formation cycle, an additional amount of lithium is extracted from the cathode by increasing the cut-off voltage of the full cell. By controlling the discharge capacity, the additional lithium extracted from the cathode is stored at the anode, ensuring that the same upper cut-off voltage is maintained in subsequent cycles.

[0056] According to a further aspect, the present invention relates to a lithium-ion battery comprising a cathode, an electrolyte and an anode, characterized in that the anode contains the electrode material according to the invention, and in that the lithium-ion battery is subjected to a formation process, wherein the formation process comprises an initial formation cycle including the following steps: a) Charging the battery to a higher final voltage V off than the nominal charge cut-off voltage of the battery, and b) Discharging the battery to the nominal discharge cut-off voltage of the battery.

[0057] In the context of the present invention, the term "formation process" refers to the one or more initial charge / discharge cycles of the lithium-ion battery, for example, at 0.1C, once the lithium-ion battery is assembled. During this process, a stable solid electrolyte interphase (SEI) layer can be formed at the anode.

[0058] According to one embodiment of the forming process according to the invention, the battery can be charged in step a) up to a final voltage which is up to 0.8 V greater than the nominal final charging voltage of the battery, preferably 0.1 - 0.5 V greater than the nominal final charging voltage of the battery, preferably 0.2 - 0.4 V greater than the nominal final charging voltage of the battery, particularly preferably about 0.3 V greater than the nominal final charging voltage of the battery.

[0059] A lithium-ion battery containing the typical cathode materials of cobalt, nickel, manganese, and aluminum typically charges to 4.20 V ± 50 mV as the nominal cut-off voltage. Some nickel-based batteries charge to 4.10 V ± 50 mV.

[0060] According to a further embodiment of the forming process according to the invention, the nominal charge end voltage of the battery can be about 4.2 V ± 50 mV, and the nominal discharge end voltage of the battery can be about 2.5 V ± 50 mV.

[0061] According to a further embodiment of the formation process according to the invention, the Coulomb efficiency of the cathode in the initial formation cycle can be 40% - 80%, preferably 50% - 70%.

[0062] According to a further embodiment of the forming process according to the invention, the forming process further comprises one or two or more forming cycles carried out in the same way as the initial one.

[0063] For conventional lithium-ion batteries, when the battery is charged to a greater cut-off voltage than the rated cut-off voltage, metallic lithium is plated on the anode, and the cathode material becomes an oxidizer, produces carbon dioxide (CO2), and increases the battery pressure.

[0064] In the case of a preferred lithium-ion battery defined below according to the invention, additional Li + -ions are intercalated into the anode having additional capacity without plating onto the anode when the battery is charged to a cut-off voltage greater than the nominal charge cut-off voltage.

[0065] In the case of another preferred lithium-ion battery defined below according to the invention, wherein the electrolyte contains one or more fluorinated carbonate compounds as a non-aqueous organic solvent, the electrochemical window of the electrolyte can be extended, and at a cut-off voltage of 5 V or even higher, battery safety can still be ensured.

[0066] To implement the present invention, an additional cathode capacitance may preferably be added to the nominal initial surface capacitance of the cathode.

[0067] In the context of the present invention, the term “nominal initial surface capacity” a of the cathode refers to the nominally intended initial surface capacity of the cathode.

[0068] In the context of the present invention, the term “surface capacity” refers to the specific surface capacity in mAh / cm 2 , the electrode capacitance per unit surface area of ​​the electrode. The term "initial cathode capacitance" refers to the initial delithiation capacity of the cathode, and the term "initial anode capacitance" refers to the initial lithiation capacity of the anode.

[0069] According to one embodiment of the lithium-ion battery according to the invention, the relative increase r of the initial surface capacity of the cathode compared to the nominal initial surface capacity a of the cathode and the final voltage V off the following linear equation with a tolerance of ± 5%, ± 10%, or ± 20% r=0.75Voff−3.134

[0070] According to a further embodiment of the lithium-ion battery according to the invention, the relative increase r of the initial surface capacity of the cathode compared to the nominal initial surface capacity a of the cathode and the final voltage V off the following quadratic equation with a tolerance of ± 5%, ± 10%, or ± 20% r=−0.7857Voff2+7.6643Voff−18.33

[0071] According to a further embodiment of the lithium-ion battery according to the invention, the nominal initial surface capacity a of the cathode and the initial surface capacity b of the anode satisfy the formulas 1 <b⋅η2 / (a⋅(1+r)−b⋅(1−η2))−ε≤1,2 preferably 1.05≤b⋅η2 / (a⋅(1+r)−b⋅(1−η2))−ε≤1.15 preferred 1.08≤b⋅η2 / (a⋅(1+r)−b⋅(1−η2))−ε≤1.12 0<ε≤((a⋅η1) / 0.6−(a−b⋅(1−η2))) / b where ε is the degree of prelithiation of the anode, and η2 is the initial Coulomb efficiency of the anode.

[0072] According to the invention, the term "prelithiation degree" ε of the anode can be calculated as (b - a x) / b, where x is the balance of the anode capacity after prelithiation and the cathode capacity. For safety reasons, the anode capacity is usually set slightly larger than the cathode capacity, and the balance of the anode capacity after prelithiation and the cathode capacity can be selected from greater than 1 to 1.2, preferably from 1.05 to 1.15, more preferably from 1.08 to 1.12, and particularly preferably about 1.1.

[0073] According to a further embodiment of the lithium-ion battery according to the invention, the degree of prelithiation of the anode can be defined as ε=((a⋅η1) / c−(a−b⋅(1−η2))) / b 0.6≤c<1 preferably 0.7≤c<1 preferred 0.7≤c≤0.9 particularly preferred 0.75≤c≤0.85 where η1 is the initial Coulomb efficiency of the cathode, and c is the depth of discharge (DoD) of the anode.

[0074] In particular, ε = (b (1 - η2) - a (1 - η1)) / b when c = 1.

[0075] According to a further embodiment of the lithium-ion battery according to the invention, the electrolyte contains one or more fluorinated carbonate compounds, preferably fluorinated cyclic or acyclic carbonate compounds, as a non-aqueous organic solvent.

[0076] According to a further embodiment of the lithium-ion battery according to the invention, the fluorinated carbonate compounds can be selected from the group consisting of fluorinated ethylene carbonate, fluorinated propylene carbonate, fluorinated dimethyl carbonate, fluorinated methyl ethyl carbonate, and fluorinated diethyl carbonate, wherein the “fluorinated” carbonate compounds can be understood to mean “monofluorinated”, “difluorinated”, “trifluorinated”, “tetrafluorinated”, and “perfluorinated” carbonate compounds.

[0077] According to a further embodiment of the lithium-ion battery according to the invention, the fluorinated carbonate compounds can be selected from the group consisting of monofluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate, 4,4,5-trifluoroethylene carbonate, 4,4,5,5-tetrafluoroethylene carbonate, 4-fluoro-4-methylethylene carbonate, 4,5-difluoro-4-methylethylene carbonate, 4-fluoro-5-methylethylene carbonate, 4,4-difluoro-5-methylethylene carbonate, 4-(fluoromethyl)-ethylene carbonate, 4-(difluoromethyl)-ethylene carbonate, 4-(trifluoromethyl)-ethylene carbonate, 4-(fluoromethyl)-4-fluoroethylene carbonate, 4-(fluoromethyl)-5-fluoroethylene carbonate, 4,4,5-trifluoro-5-methylethylene carbonate, 4-Fluoro-4,5-dimethylethylene carbonate, 4,5-difluoro-4,5-dimethylethylene carbonate, and 4,4-difluoro-5,5-dimethylethylene carbonate.

[0078] According to a further embodiment of the lithium-ion battery according to the invention, the content of the fluorinated carbonate compounds can be 10-100 vol.%, preferably 30-100 vol.%, more preferably 50-100 vol.%, particularly preferably 80-100 vol.%, based on the total non-aqueous organic solvent.

[0079] According to a further embodiment of the lithium-ion battery according to the invention, the anode active material can be selected from the group consisting of carbon, silicon, intermetallic compound of silicon, silicon oxide, silicon alloy and mixtures thereof.

[0080] According to a further embodiment of the lithium-ion battery according to the invention, the cathode active material can be selected from the group consisting of lithium nickel oxide, lithium cobalt oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium nickel cobalt manganese oxide, and mixtures thereof.

[0081] According to a further embodiment of the lithium-ion battery according to the invention, the lithium-ion battery can be further charged after the subjected forming process up to a greater final voltage V off than the nominal end-of-charge voltage of the battery and discharged to the nominal end-of-discharge voltage of the battery.

[0082] According to a further embodiment of the lithium-ion battery according to the invention, the lithium-ion battery can be further charged after the subjected forming process up to a final voltage V off charged to a voltage which is up to 0.8 V greater than the nominal final charge voltage of the battery, preferably 0.1 - 0.5 V greater than the nominal final charge voltage of the battery, preferably 0.2 - 0.4 V greater than the nominal final charge voltage of the battery, particularly preferably about 0.3 V greater than the nominal final charge voltage of the battery, and discharged to the nominal final discharge voltage of the battery.

[0083] According to a further aspect, the present invention relates to a method for producing a lithium-ion battery comprising a cathode, an electrolyte and an anode, wherein the anode contains the electrode material according to the invention, and wherein the method comprises the following steps: 1) Assembling the anode and cathode to obtain the lithium-ion battery, and 2) Subjecting the lithium-ion battery to a formation process, wherein the formation process comprises an initial formation cycle including the following steps: a) Charging the battery to a higher final voltage V off than the nominal final charge voltage of the battery, and b) Discharging the battery to the rated final discharge voltage of the battery.

[0084] For the purposes of the present invention, the term "formation process" refers to the one or more initial charge / discharge cycles of the lithium-ion battery, for example, at 0.1C, upon assembly. During this process, a stable solid electrolyte interphase (SEI) layer can be formed at the anode.

[0085] According to one embodiment of the forming process according to the invention, the battery can be charged in step a) up to a final voltage which is up to 0.8 V greater than the nominal final charging voltage of the battery, preferably 0.1 - 0.5 V greater than the nominal final charging voltage of the battery, preferably 0.2 - 0.4 V greater than the nominal final charging voltage of the battery, particularly preferably about 0.3 V greater than the nominal final charging voltage of the battery.

[0086] A lithium-ion battery containing the typical cathode materials of cobalt, nickel, manganese, and aluminum typically charges to 4.20 V ± 50 mV as the nominal cut-off voltage. Some nickel-based batteries charge to 4.10 V ± 50 mV.

[0087] According to a further embodiment of the forming process according to the invention, the nominal charge end voltage of the battery can be about 4.2 V ± 50 mV, and the nominal discharge end voltage of the battery can be about 2.5 V ± 50 mV.

[0088] According to a further embodiment of the formation process according to the invention, the Coulomb efficiency of the cathode in the initial formation cycle can be 40% - 80%, preferably 50% - 70%.

[0089] According to a further embodiment of the forming process according to the invention, the forming process further comprises one or two or more forming cycles carried out in the same way as the initial one.

[0090] To implement the present invention, an additional cathode capacitance may preferably be added to the nominal initial surface capacitance of the cathode.

[0091] In the context of the present invention, the term “nominal initial surface capacity” a of the cathode refers to the nominally intended initial surface capacity of the cathode.

[0092] In the context of the present invention, the term “surface capacity” refers to the specific surface capacity in mAh / cm 2 , the electrode capacitance per unit surface area of ​​the electrode. The term "initial cathode capacitance" refers to the initial delithiation capacity of the cathode, and the term "initial anode capacitance" refers to the initial lithiation capacity of the anode.

[0093] According to one embodiment of the method according to the invention, the relative increase r of the initial surface capacity of the cathode compared to the nominal initial surface capacity a of the cathode and the final voltage V off the following linear equation with a tolerance of ± 5%, ± 10%, or ± 20% r=0.75Voff−3.134

[0094] According to a further embodiment of the method according to the invention, the relative increase r of the initial surface capacity of the cathode compared to the nominal initial surface capacity a of the cathode and the final voltage V off the following quadratic equation with a tolerance of ± 5%, ± 10%, or ± 20% r=−0.7857Voff2+7.6643Voff−18.33

[0095] According to a further embodiment of the method according to the invention, the nominal initial surface capacity a of the cathode and the initial surface capacity b of the anode satisfy the formulas 1 <b⋅η2 / (a⋅(1+r)−b⋅(1−η2))−ε≤1,2 preferably 1.05≤b⋅η2 / (a⋅(1+r)−b⋅(1−η2))−ε≤1.15 preferred 1.08≤b⋅η2 / (a⋅(1+r)−b⋅(1−η2))−ε≤1.12 where 0<ε≤((a⋅η1) / 0.6−(a−b⋅(1−η2))) / b ε is the degree of prelithiation of the anode, and η2 is the initial Coulomb efficiency of the anode.

[0096] According to the invention, the term "prelithiation degree" ε of the anode can be calculated as (b - a x) / b, where x is the balance of the anode capacity after prelithiation and the cathode capacity. For safety reasons, the anode capacity is usually set slightly larger than the cathode capacity, and the balance of the anode capacity after prelithiation and the cathode capacity can be selected from greater than 1 to 1.2, preferably from 1.05 to 1.15, more preferably from 1.08 to 1.12, and particularly preferably about 1.1.

[0097] According to a further embodiment of the process according to the invention, the degree of prelithiation of the anode can be defined as ε=((a⋅η1) / c−(a−b⋅(1−η2))) / b 0.6≤c<1 preferably 0.7≤c<1 preferred 0.7≤c≤0.9 particularly preferred 0.75≤c≤0.85 where η1 is the initial Coulomb efficiency of the cathode, and c is the depth of discharge (DoD) of the anode. In particular, ε = (b (1 - η2) - a (1 - η1)) / b when c = 1.

[0098] According to a further embodiment of the process according to the invention, the electrolyte contains one or more fluorinated carbonate compounds, preferably fluorinated cyclic or acyclic carbonate compounds, as a non-aqueous organic solvent.

[0099] According to a further embodiment of the process according to the invention, the fluorinated carbonate compounds can be selected from the group consisting of fluorinated ethylene carbonate, fluorinated propylene carbonate, fluorinated dimethyl carbonate, fluorinated methyl ethyl carbonate, and fluorinated diethyl carbonate, where the term "fluorinated" carbonate compounds can be understood to mean "monofluorinated", "difluorinated", "trifluorinated", "tetrafluorinated", and "perfluorinated" carbonate compounds.

[0100] According to a further embodiment of the process according to the invention, the fluorinated carbonate compounds can be selected from the group consisting of monofluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate, 4,4,5-trifluoroethylene carbonate, 4,4,5,5-tetrafluoroethylene carbonate, 4-fluoro-4-methylethylene carbonate, 4,5-difluoro-4-methylethylene carbonate, 4-fluoro-5-methylethylene carbonate, 4,4-difluoro-5-methylethylene carbonate, 4-(fluoromethyl)-ethylene carbonate, 4-(difluoromethyl)-ethylene carbonate, 4-(trifluoromethyl)-ethylene carbonate, 4-(fluoromethyl)-4-fluoroethylene carbonate, 4-(fluoromethyl)-5-fluoroethylene carbonate, 4,4,5-trifluoro-5-methylethylene carbonate, 4-fluoro-4,5-dimethylethylene carbonate, 4,5-difluoro-4,5-dimethylethylene carbonate, and 4,4-difluoro-5,5-dimethylethylene carbonate.

[0101] According to a further embodiment of the process according to the invention, the content of the fluorinated carbonate compounds can be 10-100 vol.%, preferably 30-100 vol.%, more preferably 50-100 vol.%, particularly preferably 80-100 vol.%, based on the total non-aqueous organic solvent.

[0102] According to a further embodiment of the method according to the invention, the anode active material can be selected from the group consisting of carbon, silicon, intermetallic compound of silicon, silicon oxide, silicon alloy and mixtures thereof.

[0103] According to a further embodiment of the process according to the invention, the cathode active material can be selected from the group consisting of lithium nickel oxide, lithium cobalt oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium nickel cobalt manganese oxide, and mixtures thereof. Examples

[0104] The following non-limiting examples explain the production of the electrode containing the Si-based composite material according to the invention, and compare the properties of the resulting electrodes with those not produced according to the invention. The following examples illustrate various features and characteristics of the present invention and should not, however, be interpreted as a limitation of the scope of the present invention: Reference Example 1 - Production of the electrode containing a non-inventive Si-based composite material Production of a non-inventive Si-based composite material and the electrode

[0105] First, 0.08 g of silicon nanoparticles (50–200 nm) (Alfa-Aesar) were dispersed in 80 mL of Tris-HCl buffer solution (10 mM, pH 8.5) containing 0.08 g of dopamine hydrochloride (Alfa-Aesar). The particles were stirred for 2 hours, during which time dopamine polymerized in situ on the surface of the silicon-based material by air oxidation. The polydopamine-coated silicon particles were then collected by centrifugation, washed with water, and dried under vacuum for later use. The thickness of the PD coating was 1–2 nm according to TEM images. The previously prepared particles were then mixed with Super-P (40 nm, Timical) and PAA (Mv-450000, Aldrich) in water at a weight ratio of 8:1:1. After stirring for 5 hours, during which polydopamine was crosslinked to PAA, the slurry was applied to a Cu foil current collector and then further dried at 70°C under vacuum for 8 hours. The active material loading was approximately 0.5 mg / cm2 The foil was cut into Φ 12 mm sheets to assemble cells. Comparative example 1a

[0106] Comparative Example 1a was prepared similarly to Example 1, except that raw Si nanoparticles were used to prepare the electrode. Comparative example 1b

[0107] Comparative Example 1b was prepared similarly to Example 1, except that the silicon nanoparticles were changed to 0.4 g, dopamine hydrochloride to 0.2 g, and Tris-HCl buffer solution to 100 ml, respectively. Stirring lasted for 6 hours. The thickness of the PD coating was approximately 3 nm according to TEM images. The previously prepared particles were then used to fabricate the electrode, similar to Example 1. Reference Example 2 - Production of the electrode containing a non-inventive Si-based composite material

[0108] Reference Example 2 was prepared similarly to Reference Example 1, except that the active material loading in the electrode was 0.5 mg / cm 2 after about 2.0 mg / cm 2 was changed. Comparison example 2

[0109] Comparative Example 2 was prepared similarly to Comparative Example 1a, except that the active material loading in the electrode was increased from 0.5 mg / cm 2 after about 2.0 mg / cm 2 was changed. Cell assembly and electrochemical testing

[0110] The electrochemical properties of the electrodes prepared above were each tested using two-electrode button cells. The CR2016 button cells were assembled in an argon-filled glove box (MB-10 compact, MBraun) using 1 M LiPF6 / EC+DMC (1:1 by volume, ethylene carbonate (EC), dimethyl carbonate (DMC)) as the electrolyte, including 10% fluoroethylene carbonate (FEC), ENTEK ET20-26 as the separator, and pure lithium foil as the counter electrode. The cycling properties were evaluated using a LAND battery test system (Wuhan Kingnuo Electronics Co., Ltd., China) at 25°C and constant current densities. The cutoff voltage was 0.01 V versus Li / Li. + for discharge (Li-insertion) and 1.2 V against Li / Li + for charging (Li extraction). The specific capacity was calculated based on the weight of active materials.

[0111] Fig.Figure 5 shows the cycling performance of the cross-linked electrodes (Si@PD+PAA) in Reference Example 1 and Comparative Example 1b, and of the conventional electrode (Si+PAA) in Comparative Example 1a at a low mass loading. The button cell was tested at 0.1 A g -1 for the first cycle, and at 0.3 A g -1 in the next two cycles, and at 1.5 A g -1 for the following cycles between 0.01 and 1.2 V vs. Li / Li + discharged. The mass loading of active materials (Si and Si@PD) in each electrode is about 0.5 mg / cm 2 .

[0112] As from Fig. As can be seen in Figure 5, the cross-linked electrode in Reference Example 1 (curve (a)) exhibits much better cycling properties than the conventional electrode containing only PAA binder (curve (b)). The conventional electrode containing PAA binder exhibits at a high current density of 1.5 A g -1After 50 cycles, the capacity drops rapidly, and only 549 mAh / g remains after 150 cycles. In contrast, specific capacities of 2128 and 1715 mAh g are -1 achieved after 100 and 150 cycles, respectively, with the cross-linked electrode. This improvement can be attributed to the three-dimensional bonding network and improved interaction via stronger hydrogen bonding. However, if the PD coating layer is too thick, for example, 3 nm in Comparative Example 1b, the PD layer hinders electron transfer due to the low electronic conductivity of PD. Therefore, Comparative Example 1b exhibits quite low capacitance (curve (c)).

[0113] Fig. Figure 6 further shows the cycling performance of the cross-linked electrode (Si@PD+PAA) in Reference Example 2 and the conventional electrode (Si+PAA) in Comparative Example 2 at a high mass loading. The button cell was tested at 0.1 A g -1for the first cycle, and at 0.3 A g -1 in the next two cycles, and at 0.5 A g -1 for the following cycles between 0.01 and 1.2 V vs. Li / Li + discharged. The mass loading of active materials (Si and Si@PD) in each electrode is about 2.0 mg / cm 2 .

[0114] As from Fig. As can be seen in Figure 6, the cross-linked electrode offers obvious advantages even at such high active material loading (2.0 mg / cm 2 ) compared to conventional electrodes containing PAA as a binder. After 50 cycles, the specific capacity of the cross-linked electrode is 1254 mAh g -1 corresponding to 2.4 mAh / cm 2 , while the conventional electrode only has 1.1 mAh / cm 2 remains.

[0115] The cross-linked electrode has significantly improved electrochemical properties, especially cycling properties, by encapsulating the silicon particles with PD before electrode fabrication. Examples 3 to 7 - Production of the electrodes containing the Si-based composite material according to the inventionExample 3

[0116] First, 0.24 g of silicon nanoparticles (Alfa Aesar, 50-200 nm) were mixed with 0.03 g of Super-P (40 nm, Timical) and 0.03 g of PAA (Mv-450,000, Aldrich) in a weight ratio of 8:1:1 in water. After stirring for 1 hour, 0.024 mg (0.01% based on the weight of silicon nanoparticles) of the silane coupling agent γ-aminopropyltriethoxysilane (KH550) was added to the slurry. After further stirring for 4 hours, the slurry was applied to a Cu foil current collector and then dried at 70°C under vacuum for 8 hours. The active material loading was approximately 0.5 mg / cm³. 2The foil was cut into Φ12 mm sheets to assemble cells.

[0117] Example 4 was prepared similarly to Example 3, except that 0.24 mg of KH550 was incorporated into the slurry, corresponding to a 0.1 wt% ratio of KH550 to Si.

[0118] Example 5 was prepared similarly to Example 3, except that 1.2 mg of KH550 was incorporated into the slurry, corresponding to a 0.5 wt% ratio of KH550 to Si.

[0119] Example 6 was prepared similarly to Example 3, except that 2.4 mg of KH550 was incorporated into the slurry, corresponding to a 1 wt% ratio of KH550 to Si.

[0120] Example 7 was prepared similarly to Example 4, except that the active material loading in the electrode was about 2.0 mg / cm 2 fraud. Comparative Examples 3 and 4 - Production of the electrode containing the non-inventive Si-based composite material

[0121] Comparative Example 3 was prepared similarly to Example 3, except that 7.2 mg of KH550 was incorporated into the slurry, corresponding to a 3 wt% ratio of KH550 to Si. An excess amount of KH550 would impair electronic conductivity and deteriorate cell performance. Comparison example 4

[0122] The process used in Comparative Example 4 differs from the process of the present invention. The process in Comparative Example 4 involves initially coating Si with a silane coupling agent and then preparing the slurry. In contrast, the process of the present invention involves directly introducing the silane coupling agent during slurry preparation.

[0123] Specifically, in Comparative Example 4, 0.5 g of silicon nanoparticles (50-200 nm) (Alfa-Aesar) and 0.005 g (corresponding to 1 wt%) of silane coupling agent KH550 were first dispersed in 25 ml of water and then stirred for 6 hours. The silane coupling agent-coated silicon particles were then collected by centrifugation and washed with water for later use. The KH550-modified Si nanoparticles were then used to fabricate the electrode, similar to Example 3. Cell assembly and electrochemical testing

[0124] The electrochemical properties of the prepared anodes were tested using two-electrode button cells. The CR2016 button cells were assembled in an argon-filled glove box (MB-10 compact, MBraun) using 1 M LiPF6 / EC+DMC (1:1 by volume, ethylene carbonate (EC), dimethyl carbonate (DMC)) as the electrolyte, including 10% fluoroethylene carbonate (FEC), ENTEK ET20-26 as the separator, and pure lithium foil as the counter electrode. The cycling properties were evaluated using a LAND battery test system (Wuhan Kingnuo Electronics Co., Ltd., China) at 25°C and constant current densities. The cutoff voltage was 0.01 V versus Li / Li. + for discharge (Li-insertion) and 1.2 V against Li / Li + for charging (Li extraction). The specific capacity was calculated based on the weight of active materials.

[0125] Fig.Figure 7 is a graph showing the cycling characteristics of the Si electrode without KH550 (Si-PAA) prepared in Comparative Example 1a and the modified Si electrodes (Si-KH550-PAA) prepared in Examples 3-6 and Comparative Example 3 at a low mass loading. The button cell was cycled at 0.1 A g -1 for the first cycle, and at 0.3 A g -1 in the next two cycles, and at 1.5 A g -1 for the following cycles between 0.01 and 1.2 V vs. Li / Li + charged / discharged. The mass loading of active materials (Si) in each electrode is about 0.5 mg / cm 2 .

[0126] As in Fig.As shown in Figure 7, the modified electrodes Si-KH550-PAA (containing 0.01 wt%, 0.1 wt%, 0.5 wt%, and 1 wt% of KH550) exhibit much better cycling performance than both the Si electrode without KH550 in Comparative Example 1a and the modified electrode Si-KH550-PAA having a high amount of KH550 (containing 3.0 wt% of KH550) in Comparative Example 3. And even at such a high current density (1.5 A g -1 ) will have a specific capacity of more than 1690 mAh g -1 after 180 cycles for the modified electrodes Si-KH550-PAA (containing 0.01 wt%, 0.1 wt%, 0.5 wt%, and 1 wt% of KH550), while the capacity of Si-PAA was less than 900 mAh g -1 and the capacity of Si-KH550-PAA (containing 3.0 wt% of KH550) to less than 750 mAh g -1 decreases under the same conditions. This improvement may be attributable to the strong three-dimensional bonding network formed.

[0127] Fig. Figure 8 shows the cycling performance of the modified Si electrode (Si-KH550-PAA) in Example 7 and the Si electrode without KH550 (Si-PAA) in Comparative Example 1a at high loading. The button cell was tested at 0.1 A g -1 for the first cycle, and at 0.3 A g -1 in the next two cycles, and at 0.5 A g -1 for the following cycles between 0.01 and 1.2 V vs. Li / Li + charged / discharged. The mass loading of active materials (Si) in each electrode is about 2.0 mg / cm 2 .

[0128] Since the high loading is appropriate for the commercial demand for high energy density, the effects of the inventive electrodes at high loading were investigated. As in Fig. As shown in Figure 8, the modified electrode Si-KH550-PAA offers obvious advantages at such high active material loading (2.0 mg / cm 2) compared to Si-PAA. Si-KH550-PAA has a higher capacity (3276 mAh / g, corresponding to 6.6 mAh / cm 2 ) as Si-PAA (2886 mAh / g, corresponding to 5.7 mAh / cm 2 ). After 50 cycles, 61% capacity remains for Si-KH550-PAA, while the capacity of Si-PAA decreases to 29%.

[0129] Fig. Figure 9 is a graph showing the cycling characteristics of the Si electrodes prepared in Examples 4 - 6 and Comparative Example 4. In other words, Fig.Figure 9 compares the electrochemical properties of electrodes prepared by two methods: 1) the inventive method, i.e., direct introduction of KH550 during slurry preparation; 2) the method in Comparative Example 4, i.e., pretreating Si with KH550 and then using KH550-modified Si for slurry preparation. The results show that the electrodes obtained by direct introduction of KH550 exhibit better cycling performance, particularly after 40 cycles. After 100 cycles, the capacity of the electrodes obtained by method 1) of the inventive method remains at approximately 2000 mAh / g, while the electrode obtained by method 2) decreases to 1576 mAh / g.

[0130] Regardless of any theory, it is believed that by directly incorporating KH550 during slurry preparation, the hydrolyzable ends of one KH550 molecule are bonded to both the Si surface and the hydrolyzable ends of another KH550 molecule (KH550-KH550). After bonding the non-hydrolyzable ends with PAA, a highly cross-linked 3D bonding network is formed (PAA-KH550-KH550-PAA). Therefore, the bonding network is more stable. By pretreating Si with KH550, however, these small KH550-KH550 molecules are removed during washing, thus creating fewer cross-linking sites later. Therefore, the cycling performance deteriorates.

[0131] Therefore, the present invention has significantly improved electrochemical properties, particularly cycling property, by forming the three-dimensional bonding network connected via covalent bonding by incorporating silane coupling agent into the slurry during stirring. Examples P1 for prelithiation

[0132] Cathode active material: NCM-111 from BASF, and HE-NCM, prepared according to the process described in WO 2013 / 097186 A1;

[0133] Anode active material: a mixture (1:1 by weight) of silicon nanoparticles with a diameter of 50 nm from Alfa Aesar and graphite from Shenzhen Kejingstar Technology Ltd.;

[0134] Carbon additives: flake graphite KS6L and Super-P carbon black C65 from Timcal; binder: PAA, Mv = 450,000, from Sigma Aldrich;

[0135] Electrolyte: 1 M LiPF6 / EC (ethylene carbonate) + DMC (dimethyl carbonate) (1:1 after Volume);

[0136] Separator: PP / PE / PP membrane Celgard 2325. Example P1-E1:

[0137] First, anode / Li half-cells in the form of 2016 button cells were assembled in an argon-filled glove box (MB-10 compact, MBraun), using lithium metal as the counter electrode. The assembled anode / Li half-cells were discharged to the intended prelithiation degree ε, as specified in Table P1-E1, to obtain a specific amount of Li. + ions in the anode, i.e., prelithiation of the anode. The half-cells were then disassembled. The prelithiated anode and NCM-111 cathode were assembled to yield 2032 full button cells. The cycling characteristics of the full cells were evaluated at 25°C using an Arbin battery test system at 0.1C during formation and at 1C during cycling. Table P1-E1 group a η1 b η2 ε c x or F life G0 2,30 90% 2,49 87% 0 1,00 1,08 83% 339 G1 2,30 90% 2,68 87% 5,6% 0,99 1,10 86% 353 G2 2,30 90% 3,14 87% 19,5% 0,83 1,10 89% 616 G3 2,30 90% 3,34 87% 24,3% 0,77 1,10 88% 904 G4 2,30 90% 3,86 87% 34,6% 0,66 1,10 89% 1500 a is the initial delithiation capacity of the cathode [mAh / cm 2 ]; η1 is the initial Coulomb efficiency of the cathode; b is the initial lithiation capacity of the anode [mAh / cm 2 ]; η2 is the initial Coulomb efficiency of the anode; ε is the degree of prelithiation of the anode; c is the depth of discharge of the anode; x = b · (1 - ε) / a, balance of the anode and cathode capacities after prelithiation; n F the initial Coulomb efficiency of the full cell; lifetime: cycle life of the full cell (80% capacity retention).

[0138] Fig.Figure 10 shows the cycling characteristics of the full cells of groups G0, G1, G2, G3, and G4 from example P1-E1.

[0139] In group G0 with a prelithiation degree ε = 0, the capacity of the full cell decreased to 80% after 339 cycles.

[0140] For group G1, with a prelithiation degree of 5.6%, the prelithiation amount was only sufficient to compensate for the irreversible Li loss difference between the cathode and the anode. Therefore, the initial coulombic efficiency increased from 83% to 86%, while no significant improvement in cycling performance was observed.

[0141] In Group G2, with a prelithiation degree increased to 19.5%, the prelithiation amount was not only sufficient to compensate for the irreversible Li loss difference between the cathode and the anode, but an additional amount of Li was also reserved in the anode to compensate for the Li loss during cycling. Therefore, the cycle life improved significantly up to 616 cycles.

[0142] In groups G3 and G4 with further increased prelithiation degrees, Li was increasingly reserved in the anode, so that increasingly better cycling properties were achieved.

[0143] Fig.Figure 11 shows a) the volumetric energy densities and b) the gravimetric energy densities of the full cells of groups G0, G1, G2, G3, and G4 from Example P1-E1. Compared to the non-prelithiated (G0) group, G1 exhibits a higher energy density with a prelithiation degree of 5.6% due to the higher capacity. With the further increased prelithiation degree for better cycling performance, the energy density decreases to some extent, but still exhibits more than 90% of the energy density of G0 when the prelithiation degree reaches 34.6% for G4. Example P1-E2:

[0144] Example P1-E2 was performed similarly to Example P1-E1, except that HE-NCM was used as the cathode active material, and the corresponding parameters were given in Table P1-E2. Table P1-E2 group a η1 b η2 ε c x or F life G0 3,04 96% 3,25 87% 0 1,00 1,07 85% 136 G1 3,04 96% 4,09 87% 18,3% 0,90 1,10 94% 231 G2 3,04 96% 4,46 87% 26,3% 0,80 1,08 95% 316 a is the initial delithiation capacity of the cathode [mAh / cm 2 ]; η1 is the initial Coulomb efficiency of the cathode; b is the initial lithiation capacity of the anode [mAh / cm 2 ]; η2 is the initial Coulomb efficiency of the anode; ε is the degree of prelithiation of the anode; c is the depth of discharge of the anode; x = b · (1 - ε) / a, balance of the anode and cathode capacities after prelithiation; n F the initial Coulomb efficiency of the full cell; lifetime: cycle life of the full cell (80% capacity retention).

[0145] Fig.Figure 12 shows the cycling characteristics of the full cells of groups G0, G1, and G2 from example P1-E2. Fig. Figure 13 shows a) the volumetric energy densities and b) the gravimetric energy densities of the full cells from groups G0, G1, and G2 of Example P1-E2. As can be seen from Table P1-E2, the initial coulombic efficiencies of the full cells increased from 85% to 95% during prelithiation. Although larger anodes were used for prelithiation, the energy density did not decrease, or even a higher energy density was achieved, compared to non-prelithiation in G0. Furthermore, the cycling characteristics were significantly improved because the Li loss during cycling was compensated by reserved Li. Example P1-E3:

[0146] Example P1-E3 was performed similarly to Example P1-E1, except that pouch cells were assembled instead of button cells, and the corresponding prelithiation degrees ε of the anodes a) were 0 and b) 22%.

[0147] Fig. Figure 14 shows the cycling properties of the full cells from examples P1-E3 at prelithiation degrees ε of a) 0 and b) 22%. It can be seen that the cycling properties improved significantly during prelithiation. Examples P2 for prelithiation

[0148] Pouch cell size: 46 mm × 68 mm (cathode); 48 mm × 71 mm (anode);

[0149] Cathode: 96.5 wt% of NCM-111 from BASF, 2 wt% of PVDF Solef 5130 from Sovey, 1 wt% of Super-P carbon black C65 from Timcal, 0.5 wt% of conductive graphite KS6L from Timcal;

[0150] Anode: 40 wt% silicon from Alfa Aesar, 40 wt% graphite from BTR, 10 wt% NaPAA, 8 wt% conductive graphite KS6L from Timcal, 2 wt% Super-P carbon black C65 from Timcal;

[0151] Electrolyte: 1 M LiPF6 / EC + DMC (1:1 by volume, ethylene carbonate (EC), dimethyl carbonate (DMC), including 30 vol% of fluoroethylene carbonate (FEC) based on the total non-aqueous organic solvent);

[0152] Separator: PP / PE / PP membrane Celgard 2325. Comparison example P2-CE1:

[0153] A pouch cell was designed with an initial cathode capacity of 3.83 mAh / cm 2 and an initial anode capacity of 4.36 mAh / cm 2assembled in an argon-filled glove box (MB-10 compact, MBraun). The cycling performance was evaluated at 25°C using an Arbin battery test system at 0.1C during formation and at 1C during cycling, with the cell charged to the nominal end-of-charge voltage of 4.2 V and to the nominal end-of-discharge voltage of 2.5 V or to a final capacity of 3.1 mAh / cm 2 was discharged. The calculated degree of prelithiation ε of the anode was 0.

[0154] Fig. Figure 15 shows the discharge / charge curve of the cell of Comparative Example P2-CE1, where “1”, “4”, “50”, and “100” represent the 1st, 4th, 50th, and 100th cycles, respectively. Fig. Figure 17 shows the cycling characteristics of the cells from a) comparative example P2-CE1 (dashed line). Fig. Figure 18 shows the average charging voltage a) and the average discharging voltage b) of the cell from comparative example P2-CE1. Example P2-E1:

[0155] A pouch cell was designed with an initial cathode capacity of 3.73 mAh / cm 2 and an initial anode capacity of 5.17 mAh / cm 2 assembled in an argon-filled glove box (MB-10 compact, MBraun). The cycling performance was evaluated at 25°C using an Arbin battery test system at 0.1C during formation and at 1C during cycling, with the cell charged to a cut-off voltage of 4.5V, which was 0.3V higher than the nominal charge cut-off voltage, and to the nominal discharge cut-off voltage of 2.5V or to a final capacity of 3.1mAh / cm 2 was discharged. The calculated degree of prelithiation ε of the anode was 21%.

[0156] Fig. Figure 16 shows the discharge / charge curve of the cell from example P2-E1, where “1”, “4”, “50”, and “100” represent the 1st, 4th, 50th, and 100th cycles, respectively. Fig.Figure 17 shows the cycle properties of the cells from b) example P2-E1 (solid line). Fig. Figure 19 shows the average charging voltage a) and the average discharging voltage b) of the cell from example P2-E1.

Claims

[1] A lithium-ion battery comprising a cathode, an electrolyte and an anode, wherein the initial surface capacity a of the cathode and the initial surface capacity b of the anode satisfy the formulas 1<(b⋅(1−ε) / a)≤1.2 preferably 1.05≤(b⋅(1−ε) / a)≤1.15 preferred 1.08≤(b⋅(1−ε) / a)≤1.12 0<ε≤((a⋅η1) / 0.6−(a−b⋅(1−η2))) / b where ε is the degree of prelithiation of the anode, η1 is the initial Coulomb efficiency of the cathode, and η2 is the initial Coulomb efficiency of the anode, wherein the electrode material of the anode contains a silicon-based composite material with a three-dimensional bonding network and improved interaction between binder and silicon-based material, wherein the silicon-based composite material is produced by a process comprising introducing silane coupling agent with amine and / or imine groups into a slurry containing silicon-based material, a carboxyl-containing binder, and conductive carbon, while stirring, wherein the amount of the silane coupling agent having amine and / or imine groups is 0.01 - 2.5 wt.%, based on the weight of the silicon-based material. [2] Lithium-ion battery according to claim 1, characterized by , that ε=((a⋅η1) / c−(a−b⋅(1−η2))) / b 0.6≤c<1 preferably 0.7≤c<1 preferred 0.7≤c≤0.9 particularly preferred 0.75≤c≤0.85 where c is the depth of discharge of the anode. [3] Lithium-ion battery comprising a cathode, an electrolyte and an anode, characterized by that the lithium-ion battery is subjected to a formation process, wherein the formation process comprises an initial formation cycle including the following steps: a) Charging the battery to a final voltage V off which is greater than the nominal final charging voltage of the battery, preferably up to 0.8 V greater than the nominal final charging voltage of the battery, preferably 0.1 - 0.5 V greater than the nominal final charging voltage of the battery, particularly preferably 0.2 - 0.4 V greater than the nominal final charging voltage of the battery, in particular about 0.3 V greater than the nominal final charging voltage of the battery, and b) Discharging the battery to the rated final discharge voltage of the battery, wherein the electrode material of the anode contains a silicon-based composite material with a three-dimensional bonding network and improved interaction between binder and silicon-based material, wherein the silicon-based composite material is produced by a process comprising introducing silane coupling agent with amine and / or imine groups into a slurry containing silicon-based material, a carboxyl-containing binder, and conductive carbon, while stirring, wherein the amount of the silane coupling agent having amine and / or imine groups is 0.01 - 2.5 wt.%, based on the weight of the silicon-based material. [4] Lithium-ion battery according to claim 3, characterized by that the relative increase r of the initial surface capacity of the cathode compared to the nominal initial surface capacity a of the cathode and the final voltage V offsatisfy the following linear equation with a tolerance of ± 10% r=0.75Voff−3.134 [5] Lithium-ion battery according to claim 3, characterized by that the relative increase r of the initial surface capacity of the cathode compared to the nominal initial surface capacity a of the cathode and the final voltage V off satisfy the following quadratic equation with a tolerance of ± 10% r=−0.7857Voff2+7.6643Voff−18.33 [6] Lithium-ion battery according to one of claims 3 to 5, characterized by that the nominal initial surface capacity a of the cathode and the initial surface capacity b of the anode satisfy the formulas 1 <b⋅η2 / (a⋅(1+r)−b⋅(1−η2))−ε≤1,2 preferably 1.05≤b⋅η2 / (a⋅(1+r)−b⋅(1−η2))−ε≤1.15 preferred 1.08≤b⋅η2 / (a⋅(1+r)−b⋅(1−η2))−ε≤1.12 0<ε≤((a⋅η1) / 0.6−(a−b⋅(1−η2))) / b where ε is the degree of prelithiation of the anode, and η2 is the initial Coulomb efficiency of the anode. [7] Lithium-ion battery according to one of claims 3 to 6, characterized by , that ε=((a⋅η1) / c−(a−b⋅(1−η2))) / b (III), 0.6≤c<1 preferably 0.7≤c<1 preferred 0.7≤c≤0.9 particularly preferred 0.75≤c≤0.85 where η1 is the initial Coulomb efficiency of the cathode, and c is the depth of discharge of the anode. [8] Lithium-ion battery according to one of claims 3 to 7, characterized by that the electrolyte contains one or more fluorinated carbonate compounds, preferably fluorinated cyclic or acyclic carbonate compounds, as a non-aqueous organic solvent. [9] Lithium-ion battery according to one of claims 3 to 8, characterized by that the lithium-ion battery continues to charge up to a final voltage V after the formation process has been subjected to. offcharged which is greater than the nominal final charging voltage of the battery, preferably up to 0.8 V greater than the nominal final charging voltage of the battery, preferably 0.1 - 0.5 V greater than the nominal final charging voltage of the battery, particularly preferably 0.2 - 0.4 V greater than the nominal final charging voltage of the battery, in particular approximately 0.3 V greater than the nominal final charging voltage of the battery, and discharged up to the nominal final discharging voltage of the battery. [10] Lithium-ion battery according to one of claims 1 to 5, wherein the amount of the silane coupling agent is 0.05 - 2.0 wt%, preferably 0.1 - 2.0 wt%, and particularly preferably 0.1 - 1.0%, based on the weight of the silicon-based material. [11] A lithium-ion battery according to any one of claims 1 to 5, wherein the carboxyl-containing binder is selected from the group consisting of polyacrylic acid, carboxymethylcellulose, sodium alginate, copolymers thereof, and combinations thereof. [12] The lithium-ion battery according to any one of claims 1 to 5, wherein the silane coupling agent having amine and / or imine groups is one or more selected from the group consisting of γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, N,N-(aminopropyltriethoxy)silane, γ-trimethoxysilylpropyldiethylenetriamine, γ-divinyltriamine-propylmethyldimethoxysilane, bis-γ-trimethoxysilylpropylamine, aminoneohexyltrimethoxysilane, and aminoneohexylmethyldimethoxysilane. [13] A method for producing a lithium-ion battery comprising a cathode, an electrolyte and an anode, the method comprising the following steps: 1) Prelithiation of the anode active material or the anode up to a degree of prelithiation ε, and 2) Assembling the anode and cathode to obtain the lithium-ion battery, characterized by that the initial surface capacity a of the cathode, the initial surface capacity b of the anode and the degree of prelithiation ε satisfy the formulas 1<(b⋅(1−ε) / a)≤1.2 preferably 1.05≤(b⋅(1−ε) / a)≤1.15 preferred 1.08≤(b⋅(1−ε) / a)≤1.12 0<ε≤((a⋅η1) / 0.6−(a−b⋅(1−η2))) / b where ε is the degree of prelithiation of the anode, η1 is the initial Coulomb efficiency of the cathode, and η2 is the initial Coulomb efficiency of the anode, wherein the electrode material of the anode contains a silicon-based composite material with a three-dimensional bonding network and improved interaction between binder and silicon-based material, wherein the silicon-based composite material is produced by a process comprising introducing silane coupling agent with amine and / or imine groups into a slurry containing silicon-based material, a carboxyl-containing binder, and conductive carbon, while stirring, wherein the amount of the silane coupling agent having amine and / or imine groups is 0.01 - 2.5 wt.%, based on the weight of the silicon-based material. [14] Method according to claim 13, characterized by , that ε=((a⋅η1) / c−(a−b⋅(1−η2))) / b 0.6≤c<1 preferably 0.7≤c<1 preferred 0.7≤c≤0.9 particularly preferred 0.75≤c≤0.85 where c is the depth of discharge of the anode. [15] A method for producing a lithium-ion battery comprising a cathode, an electrolyte and an anode, the method comprising the following steps: 1) Assembling the anode and cathode to obtain the lithium-ion battery, and 2) Subjecting the lithium-ion battery to a formation process, wherein the formation process comprises an initial formation cycle including the following steps: a) Charging the battery to a final voltage V off which is greater than the nominal final charging voltage of the battery, preferably up to 0.8 V greater than the nominal final charging voltage of the battery, preferably 0.1 - 0.5 V greater than the nominal final charging voltage of the battery, particularly preferably 0.2 - 0.4 V greater than the nominal final charging voltage of the battery, in particular about 0.3 V greater than the nominal final charging voltage of the battery, and b) Discharging the battery to the rated final discharge voltage of the battery, wherein the electrode material of the anode contains a silicon-based composite material with a three-dimensional bonding network and improved interaction between binder and silicon-based material, wherein the silicon-based composite material is produced by a process comprising introducing silane coupling agent with amine and / or imine groups into a slurry containing silicon-based material, a carboxyl-containing binder, and conductive carbon, while stirring, wherein the amount of the silane coupling agent having amine and / or imine groups is 0.01 - 2.5 wt.%, based on the weight of the silicon-based material. [16] Method according to claim 15, characterized by that the relative increase r of the initial surface capacity of the cathode compared to the nominal initial surface capacity a of the cathode and the final voltage Voff satisfy the following linear equation with a tolerance of ± 10% r=0.75Voff−3.134 [17] Method according to claim 15, characterized by that the relative increase r of the initial surface capacity of the cathode compared to the nominal initial surface capacity a of the cathode and the final voltage V off satisfy the following quadratic equation with a tolerance of ± 10% r=−0.7857Voff2+7.6643Voff−18.33 [18] Method according to one of claims 14 to 16, characterized by that the nominal initial surface capacity a of the cathode and the initial surface capacity b of the anode satisfy the formulas 1 <b⋅η2 / (a⋅(1+r)−b⋅(1−η2))−ε≤1,2 preferably 1.05 <b⋅η2 / (a⋅(1+r)−b⋅(1−η2))−ε≤1,15 preferred 1.08 <b⋅η2 / (a⋅(1+r)−b⋅(1−η2))−ε≤1,12 0<ε≤((a⋅η1) / 0.6−(1−b⋅(1−η2))) / b where ε is the degree of prelithiation of the anode, and η2 is the initial Coulomb efficiency of the anode. [19] Method according to one of claims 15 to 18, characterized by , that ε=((a⋅η1) / c−(a−b⋅(1−η2))) / b 0.6≤c<1 preferably 0.7≤c<1 preferred 0.7≤c≤0.9 particularly preferred 0.75≤c≤0.85 where η1 is the initial Coulomb efficiency of the cathode, and c is the depth of discharge of the anode. [20] Method according to one of claims 15 to 19, characterized by that the electrolyte contains one or more fluorinated carbonate compounds, preferably fluorinated cyclic or acyclic carbonate compounds, as a non-aqueous organic solvent. [21] A method according to any one of claims 13 to 17, wherein the amount of the silane coupling agent is 0.05 - 2.0 wt%, preferably 0.1 - 2.0 wt%, and particularly preferably 0.1 - 1.0%, based on the weight of the silicon-based material. [22] A method according to any one of claims 13 to 17, wherein the carboxyl-containing binder is selected from the group consisting of polyacrylic acid, carboxymethylcellulose, sodium alginate, copolymers thereof and combinations thereof. [23] The method according to any one of claims 13 to 17, wherein the silane coupling agent having amine and / or imine groups is one or more selected from the group consisting of γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, N,N-(aminopropyltriethoxy)silane, γ-trimethoxysilylpropyldiethylenetriamine, γ-divinyltriamine-propylmethyldimethoxysilane, bis-γ-trimethoxysilylpropylamine, aminoneohexyltrimethoxysilane, and aminoneohexylmethyldimethoxysilane.

Images