CN113363419A - Negative pole piece and preparation method and application thereof - Google Patents

Negative pole piece and preparation method and application thereof Download PDF

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CN113363419A
CN113363419A CN202110696472.5A CN202110696472A CN113363419A CN 113363419 A CN113363419 A CN 113363419A CN 202110696472 A CN202110696472 A CN 202110696472A CN 113363419 A CN113363419 A CN 113363419A
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lithium ion
ion battery
pole piece
layer
lithium
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CN113363419B (en
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从长杰
高秀玲
曹迎倩
张越超
吕飞
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Tianjin EV Energies Co Ltd
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • Y02E60/10—Energy storage using batteries
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Abstract

The invention provides a negative pole piece and a preparation method and application thereof; the negative pole piece comprises a current collector, an active substance layer and a Ti-containing oxide solid electrolyte layer which are sequentially arranged; through the design of a three-layer structure and the special selection of each layer of structure, when the negative pole piece is applied to the lithium ion battery, a layer of compact passivation film can be formed on the surface of the negative pole piece, so that the lithium dendrite is prevented from piercing a lithium ion battery diaphragm to cause the short circuit of the battery, and the safety performance of the lithium ion battery is improved; the negative pole piece is matched with the preparation method of the lithium ion battery provided by the invention, so that the dissolution of Mn ions in the positive pole material can be inhibited, the using amount of the electrolyte is reduced, the safety performance of the lithium ion battery is further improved, and the preparation method has important research significance.

Description

Negative pole piece and preparation method and application thereof
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to a negative pole piece and a preparation method and application thereof.
Background
At present, a lithium ion battery mainly uses liquid electrolyte, but the liquid battery has the problems of poor safety performance, flammability, large interface resistance, weak ion transmission capability, poor performance such as poor charge and discharge performance, poor multiplying power circulation performance and the like at normal temperature, and further cannot realize commercial production.
The interface problem which is difficult to solve in the all-solid-state battery is the biggest obstacle for limiting the practical application of the all-solid-state battery, the polymer electrolyte has good flexibility and can ensure better interface contact in the battery, the oxide electrolyte has higher lithium ion conductivity and safety performance, and the combination of the polymer electrolyte and the oxide electrolyte is hopeful to obtain the all-solid-state battery with electrochemical performance meeting the actual requirement. Currently, a PEO-based polymer electrolyte is mostly used for assembling an all-solid-state battery in research, the PEO-based polymer electrolyte has the advantages of good low-voltage stability, low interface impedance and the like, but is oxidized and decomposed at a voltage of more than 4V, and only a lithium iron phosphate material can be matched with a common positive electrode material, so that the energy density of the battery is limited. Meanwhile, the conductivity of the PEO-based polymer electrolyte is low, and the assembled all-solid-state battery can only operate at high temperature and low rate.
Therefore, research into solid state lithium ion batteries is still ongoing. CN112467117A discloses a graphite composite material coated by lithium titanium aluminum phosphate, a preparation method thereof and a battery negative electrode. The lithium titanium aluminum phosphate coated graphite composite material comprises: an inner core, the material of the inner core comprising graphite; the shell layer is coated outside the inner core, and the material of the shell layer comprises titanium aluminum lithium phosphate and carbon; and the passivation layer is coated outside the shell. The titanium aluminum lithium phosphate and the carbon are coated outside the graphite, so that the conductivity can be improved, the titanium aluminum lithium phosphate has higher lithium ion conductivity, the transmission efficiency of lithium ions can be improved, and compared with other materials, the titanium aluminum lithium phosphate has the characteristics of stable structure, strong chemical stability, good cycle performance and the like. The passivation layer has a passivation effect on the lithium titanium aluminum phosphate, reduces the occurrence of side reactions of the lithium titanium aluminum phosphate, and improves the storage performance and the cycle performance of the lithium titanium aluminum phosphate, thereby improving the transmission efficiency, the rate capability and the safety performance of lithium ions of the lithium titanium aluminum phosphate coated graphite composite material. However, the preparation process of the battery is complex, high in cost and long in manufacturing period, and is not beneficial to large-scale and large-scale production and application.
CN111384436A discloses an all-solid-state lithium ion battery with a composite negative electrode plate coated with solid electrolyte slurry and a preparation method thereof, the invention firstly uses water-based polymer solid electrolyte to prepare the composite negative electrode plate, then the composite negative electrode plate is coated with slurry mixed with oily organic binder and high oxide solid electrolyte content to be dried and rolled, and then the composite positive electrode is assembled with a composite positive electrode prepared from high-pressure resistant oily polymer electrolyte. And adding a small amount of organic solvent between the positive electrode and the negative electrode in the battery assembly process to wet an interface, and drying the organic solvent before packaging the battery. The all-solid-state battery assembled by the method has excellent safety performance, high energy density and good cycle performance. CN112670450A discloses a negative pole piece for a solid-state battery and a preparation method and application thereof; the negative pole piece comprises a copper foil, a lithium metal layer, a lithium nitride layer and an organic-inorganic composite layer which are sequentially stacked. According to the invention, ultrathin and uniform electroplated lithium metal is used as a base material, surface modification is carried out on the surface of the ultrathin and uniform electroplated lithium metal through nitrogen so that the lithium metal is uniformly deposited, short circuit is prevented, the loss of a lithium source in the circulation process is slowed down, and then an organic-inorganic composite coating is compounded on the surface of the treated lithium metal so that the lithium metal deposited by charging deposition is more uniformly and compactly deposited, the occurrence of short circuit is effectively inhibited, and the interface reaction generated by direct contact of the lithium metal and an electrolyte is inhibited, so that the circulation performance is improved; however, the solid-state batteries prepared by the two methods still have certain potential safety hazards in use.
Therefore, the development of a negative electrode plate capable of forming a dense passivation film on the surface when in use is a technical problem which is urgently needed to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a negative pole piece and a preparation method and application thereof, wherein the negative pole piece comprises a current collector, an active substance layer and a Ti-containing oxide solid electrolyte layer which are sequentially arranged; through three-layer structure design and special selection of materials in each layer of structure, when the obtained negative pole piece is applied to the lithium ion battery, a layer of compact passivation film is formed on the surface of the pole piece, the passivation film can avoid safety problems of battery short circuit, explosive combustion and the like caused by the fact that lithium dendrites pierce through a lithium ion battery diaphragm, and further safety performance of the lithium ion battery is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a negative electrode plate, which includes a current collector, an active material layer, and a Ti-containing oxide solid electrolyte layer, which are sequentially disposed.
The schematic cross-sectional structure of the negative electrode plate provided by the invention is shown in fig. 1, wherein 1 represents a current collector, 2 represents an active material layer, and 3 represents a Ti-containing oxide solid electrolyte layer; according to the negative pole piece provided by the invention, through the design of a three-layer structure, and the specific selection of materials in each layer, a compact passivation film can be formed on the surface of the negative pole piece when the negative pole piece is applied to a lithium ion battery, the passivation film can effectively prevent the lithium ion battery short circuit problem caused by the growth of lithium dendrites, and can also reduce the occurrence of side reactions of an oxide solid electrolyte layer material containing Ti, so that the long-term cycle performance, the high-temperature cycle performance and the safety performance of the lithium ion battery can be effectively improved, and the negative pole piece has important research significance.
The Ti-containing oxide material of the Ti-containing oxide solid electrolyte layer in the negative pole piece has high lithium ion conductivity, so that the transmission efficiency of lithium ions can be improved.
Preferably, the thickness of the negative electrode plate is 80-200 μm, such as 100 μm, 120 μm, 140 μm, 160 μm or 180 μm, and the specific values therebetween are limited by space and for brevity, and the specific values included in the range are not exhaustive.
Preferably, the current collector comprises a copper foil.
Preferably, the thickness of the active material layer is 70 to 190 μm, such as 80 μm, 90 μm, 100 μm, 120 μm, 140 μm, 160 μm or 180 μm, and specific values therebetween, which are not exhaustive for the invention and are included in the range for brevity. .
Preferably, the material of the active material coating layer includes a combination of a negative electrode active material, a conductive agent, and a binder.
Preferably, the negative active material includes a silicon carbon material.
Preferably, the conductive agent comprises carbon black.
Preferably, the binder comprises CMC and/or SBR.
Preferably, the thickness of the Ti-containing oxide solid electrolyte layer is 2 to 5 μm, such as 2.3 μm, 2.6 μm, 2.9 μm, 3.3 μm, 3.6 μm, 3.9 μm, 4.3 μm, 4.6 μm, or 4.9 μm, and specific values therebetween, which are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific values included in the range.
Preferably, the raw material for preparing the Ti oxide-containing solid electrolyte layer includes a Ti oxide-containing slurry.
Preferably, the Ti-containing oxide substance slurry comprises the following components in parts by weight: 80-95 parts of Ti oxide-containing solid electrolyte, 0.5-3 parts of binder and 15-70 parts of solvent.
The Ti-containing oxide may be 82 parts by weight, 84 parts by weight, 86 parts by weight, 88 parts by weight, 90 parts by weight, 92 parts by weight, or 94 parts by weight, and specific values therebetween are not exhaustive for the purpose of brevity and clarity.
The binder may be present in an amount of 0.7 parts by weight, 0.9 parts by weight, 1.1 parts by weight, 1.3 parts by weight, 1.6 parts by weight, 1.9 parts by weight, 3.3 parts by weight, 3.6 parts by weight, or 3.9 parts by weight, and the specific values therebetween are not exhaustive for the purpose of brevity and clarity.
The solvent may be 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, or 65 parts by weight, and specific points therebetween are not exhaustive for the invention and are included for brevity.
Preferably, the binder comprises any one of polyvinylidene fluoride, CMC or SBR or a combination of at least two thereof.
Preferably, the solvent comprises N-methylpyrrolidone.
Preferably, the Ti-containing oxide includes any one of lithium titanium phosphate, lithium titanium aluminum phosphate, or lithium lanthanum titanate, or a combination of at least two thereof.
Preferably, the Ti-containing oxide has a particle size of 1 to 100nm, such as 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm or 90nm, and the specific values therebetween are not exhaustive for the invention and are included in the scope for brevity.
Preferably, the Ti-containing oxide slurry is prepared by a method comprising the steps of:
(A1) mixing a binder and a solvent to obtain a binder glue solution;
(A2) and (D) mixing the binder glue solution obtained in the step (A1) with Ti-containing oxide to obtain the Ti-containing oxide slurry.
In a second aspect, the present invention provides a method for preparing the negative electrode plate according to the first aspect, where the method includes: and sequentially coating the preparation raw material of the active substance layer and the Ti-containing oxide slurry on the surface of the current collector to obtain the negative pole piece.
In a third aspect, the present invention provides a lithium ion battery, including the negative electrode plate, the positive electrode plate, the separator and the electrolyte according to the first aspect.
In a fourth aspect, the present invention provides a method for preparing the lithium ion battery according to the third aspect, wherein the method comprises the following steps:
(1) laminating and packaging the positive pole piece, the negative pole piece and the diaphragm to obtain an initial lithium ion battery;
(2) baking the initial lithium ion battery obtained in the step (1), injecting electrolyte, pre-charging, aging and forming to obtain a formed lithium ion battery;
(3) and (3) carrying out clamp formation on the formed lithium ion battery obtained in the step (2) to obtain the lithium ion battery.
Preferably, the aging temperature in the step (2) is 35-65 ℃, for example, 38 ℃, 41 ℃, 45 ℃, 48 ℃, 51 ℃, 55 ℃, 58 ℃, 61 ℃ or 63 ℃, and the specific values therebetween are limited by the space and the conciseness, and the invention does not exhaust the specific values included in the range, and more preferably 35-45 ℃.
Preferably, the aging time in step (2) is 70-74 h, such as 70.5h, 71h, 71.5h, 72h, 72.5h, 73h or 73.5h, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive of the specific values included in the range.
Preferably, the method of forming the jig in step (3) comprises: the reaction is carried out at a temperature of 40 to 50 ℃ (e.g., 41 ℃, 42 ℃, 43 ℃, 44 ℃, 45 ℃, 46 ℃, 47 ℃, 48 ℃ or 49 ℃) for 4 to 25 hours (e.g., 9 hours, 13 hours, 15 hours, 17 hours, 19 hours, 21 hours, 23 hours, 24 hours or 25 hours) and at a current of 0.01 to 0.5 ℃ (e.g., 0.05C, 0.1C, 0.15C, 0.2C, 0.25C, 0.3C, 0.35C, 0.4C or 0.45C), at a temperature of 30 to 40 ℃ (e.g., 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃ or 39 ℃) and at a current of 0.5 to 2C (e.g., 0.7C, 0.8C, 0.9C, 1.3C, 1.5C, 1.7C or 1.9C) for 10 to 100 hours (e.g., 10 hours, 20 hours, 30 hours, 90 hours, 60 hours, 100 hours, 10 hours, 30 hours, 90 hours, 100 hours, etc.). As a preferred technical solution of the present invention, the preparation method of the lithium ion battery provided by the present invention comprises: the lithium ion battery cathode plate is prepared by the steps of reacting for 4-25h at the temperature of 40-50 ℃ and the current of 0.01-0.5C, and reacting for 10-100 h at the temperature of 30-40 ℃ and the current of 0.5-2C, and the steps are matched with the cathode plate provided by the first aspect, so that the lithium ion battery cathode plate is more beneficial to increasing the consumption of electrolyte, and the dissolution of Mn ions in the cathode plate can be inhibited; the safety performance and the electrical performance of the lithium ion battery are further improved.
Preferably, the clamp is formed with a clamp pressure of 50-1000 kg, such as 100kg, 200kg, 300kg, 400kg, 500kg, 600kg, 700kg, 800kg or 900kg, and specific values therebetween, which are not exhaustive and included in the scope for brevity.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) laminating and packaging the positive pole piece, the negative pole piece and the diaphragm to obtain an initial lithium ion battery;
(2) baking the initial lithium ion battery obtained in the step (1), injecting electrolyte, pre-charging, aging and forming to obtain a formed lithium ion battery;
(3) and (3) converting the lithium ion battery obtained in the step (2) into a lithium ion battery for 4-25h at the temperature of 40-50 ℃ and the current of 0.01-0.5C, and converting into a lithium ion battery for 10-100 h at the temperature of 30-40 ℃ and the current of 0.5-2C to obtain the lithium ion battery.
In a fifth aspect, the present invention provides a use of the lithium ion battery according to the third aspect in the automotive field.
Compared with the prior art, the invention has the following beneficial effects:
(1) the negative pole piece provided by the invention comprises a current collector, an active substance layer and a Ti-containing oxide solid electrolyte layer which are sequentially arranged; through the design of the three-layer structure, each layer of structure is specially selected, so that when the negative pole piece is applied to the lithium ion battery, a layer of compact passivation film can be formed on the surface of the negative pole piece, the passivation film can avoid safety problems such as battery short circuit, explosion and combustion and the like caused by the fact that the lithium dendrite pierces the lithium ion battery diaphragm, and the safety performance of the lithium ion battery is improved.
(2) The negative pole piece and the preparation method of the lithium ion battery provided by the invention can inhibit the dissolution of Mn ions in the positive pole material, reduce the using amount of electrolyte and further improve the safety performance of the lithium ion battery.
(3) Specifically, the liquid retention capacity of the lithium ion battery prepared by the negative electrode plate provided by the invention is 119-125 g, the internal resistance (DCR) is 1.28-1.3 m omega, the failure time at 130 ℃ is more than 2.2h, the cycle performance can reach 2320-2503 weeks, and the energy density is 280-291 Wh/kg.
Drawings
Fig. 1 is a schematic cross-sectional structure diagram of a negative electrode plate provided by the present invention, wherein 1-a current collector, 2-an active material layer and 3-a Ti-containing oxide solid electrolyte layer;
fig. 2 is a scanning electron microscope image of a negative electrode sheet after disassembly of the lithium ion battery provided in application example 1;
fig. 3 is a scanning electron microscope image of the composite separator after the lithium ion battery provided in application example 1 is disassembled;
fig. 4 is a scanning electron microscope image of a negative electrode tab after disassembly of the lithium ion battery provided in comparative application example 3;
fig. 5 is a scanning electron microscope image of the composite separator disassembled from the lithium ion battery provided in comparative application example 3.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
The lithium aluminum titanium phosphate slurry comprises the following components in parts by weight:
Figure BDA0003128623100000081
Figure BDA0003128623100000091
the preparation method of the lithium aluminum titanium phosphate slurry provided by the preparation example comprises the following steps:
(1) mixing CMC, SBR and NMP to obtain a binder glue solution;
(2) and (2) mixing the binder glue solution obtained in the step (1) with lithium titanium aluminum phosphate to obtain the lithium titanium aluminum phosphate slurry.
Preparation example 2
The titanium lithium phosphate slurry comprises the following components in parts by weight:
Figure BDA0003128623100000092
the preparation method of the lithium titanium phosphate slurry provided by the preparation example comprises the following steps:
(1) mixing CMC, SBR and NMP to obtain a binder glue solution;
(2) and (2) mixing the binder glue solution obtained in the step (1) with lithium titanium phosphate to obtain the lithium titanium aluminum phosphate slurry.
Preparation example 3
The lanthanum lithium titanate slurry comprises the following components in parts by weight:
Figure BDA0003128623100000093
the preparation method of the lanthanum lithium titanate slurry provided by the preparation example comprises the following steps:
(1) mixing CMC, SBR and NMP to obtain a binder glue solution;
(2) and (2) mixing the binder glue solution obtained in the step (1) with the lanthanum lithium titanate to obtain the lanthanum lithium titanate slurry.
Preparation example 4
A composite diaphragm comprises a Ti oxide-containing solid electrolyte layer, a first Ti oxide-containing solid electrolyte/ceramic oxide matching layer, a polyolefin layer and a second Ti oxide-containing solid electrolyte/ceramic oxide matching layer which are arranged in sequence;
wherein, the thickness of the Ti-containing oxide solid electrolyte layer is 1.5 μm, and the material is titanium aluminum lithium phosphate;
the thickness of the first Ti-containing oxide solid electrolyte/ceramic oxide matching layer is 2 microns, and the materials are titanium aluminum lithium phosphate and aluminum oxide with the mass ratio of 1: 50;
the polyolefin layer has a thickness of 9 μm and is made of polyethylene (model SU09, Hebei Jinli New energy science and technology Co., Ltd.);
the thickness of the second Ti-oxide-containing solid electrolyte/ceramic oxide matching layer is 2.5 mu m, and the materials are lithium aluminum titanium phosphate and aluminum oxide with the ratio of 1: 50;
the preparation method of the composite diaphragm provided by the preparation example comprises the following steps:
(1) coating a material of a first Ti oxide-containing solid electrolyte/ceramic oxide matching layer and a preparation raw material of a second Ti oxide-containing solid electrolyte/ceramic oxide matching layer on two sides of the polyethylene layer respectively to obtain a composite layer;
(2) and (2) coating titanium aluminum lithium phosphate on the surface of the first Ti oxide-containing solid electrolyte/ceramic oxide collocation layer of the composite layer obtained in the step (1) to obtain the composite diaphragm.
Preparation example 5
A composite diaphragm comprises a Ti oxide-containing solid electrolyte layer, a first Ti oxide-containing solid electrolyte/ceramic oxide matching layer, a polyolefin layer and a second Ti oxide-containing solid electrolyte/ceramic oxide matching layer which are arranged in sequence;
wherein, the thickness of the Ti-containing oxide solid electrolyte layer is 1.5 μm, and the material is titanium lithium phosphate;
the thickness of the first Ti-containing oxide solid electrolyte/ceramic oxide matching layer is 2 microns, and the materials are titanium lithium phosphate and aluminum oxide with the mass ratio of 1: 50;
the polyolefin layer has a thickness of 9 μm and is made of polyethylene (model SU09, Hebei Jinli New energy science and technology Co., Ltd.);
the thickness of the second Ti-containing oxide solid electrolyte/ceramic oxide matching layer is 2.5 mu m, and the materials are titanium lithium phosphate and aluminum oxide with the mass ratio of 1: 19;
the preparation method of the composite separator provided in this preparation example is the same as that of preparation example 4.
Preparation example 6
A composite diaphragm comprises a Ti oxide-containing solid electrolyte layer, a first Ti oxide-containing solid electrolyte/ceramic oxide matching layer, a polyolefin layer and a second Ti oxide-containing solid electrolyte/ceramic oxide matching layer which are arranged in sequence;
wherein, the thickness of the Ti-containing oxide solid electrolyte layer is 1.5 μm, and the material is lanthanum lithium titanate;
the thickness of the first Ti-containing oxide solid electrolyte/ceramic oxide matching layer is 2 mu m, and the materials are lanthanum lithium titanate and aluminum oxide with the mass ratio of 1: 50;
the polyolefin layer has a thickness of 9 μm and is made of polyethylene (model SU09, Hebei Jinli New energy science and technology Co., Ltd.);
the thickness of the second Ti-containing oxide solid electrolyte/ceramic oxide matching layer is 2.5 mu m, and the materials are lanthanum lithium titanate and aluminum oxide with the mass ratio of 1: 19;
the preparation method of the composite separator provided in this preparation example is the same as that of preparation example 4.
Example 1
A negative pole piece is shown in figure 1, and comprises a current collector 1, an active material layer 2 and a Ti-containing oxide solid electrolyte layer 3;
wherein, the current collector 1 is a copper foil with the thickness of 8 μm;
the thickness of the active material coating layer 2 is 175 μm, and the raw materials are active material slurry (the preparation method comprises mixing a silicon carbon material, carbon black, a binder (CMC and SBR in a mass ratio of 1.3: 2), CNTs and NMP in a mass ratio of 90:3:3:4: 3);
the thickness of the solid electrolyte layer 3 was 3 μm, and a titanium aluminum lithium phosphate slurry (preparation example 1) was prepared as a raw material;
the preparation method of the negative electrode plate provided by the embodiment comprises the following steps: and sequentially coating active substance slurry and titanium aluminum lithium phosphate slurry on the surface of the copper foil to obtain the negative pole piece.
Example 2
A negative electrode sheet differing from example 1 only in that the lithium titanium phosphate slurry obtained in preparation example 2 was used instead of the lithium aluminum titanium phosphate slurry obtained in preparation example 1 as a raw material for preparing a solid electrolyte layer, and the other structures, parameters and preparation methods were the same as those of example 1.
Example 3
A negative electrode sheet differing from example 1 only in that the lanthanum lithium titanate slurry obtained in production example 3 was used instead of the titanium aluminum lithium phosphate slurry obtained in production example 1 as a raw material for producing a solid electrolyte layer, and the other structures, parameters and production methods were the same as in example 1.
Example 4
A negative electrode plate was distinguished from example 1 in that the thickness of the solid electrolyte layer was 2 μm, the thickness of the active material coating was 175 μm, and the other structures, parameters and preparation methods were the same as in example 1.
Example 5
A negative electrode plate was distinguished from example 1 in that the thickness of the solid electrolyte layer was 5 μm, the thickness of the active material coating was 175 μm, and the other structures, parameters and preparation methods were the same as in example 1.
Example 6
A negative electrode plate was distinguished from example 1 in that the thickness of the solid electrolyte layer was 1 μm, the thickness of the active material coating was 175 μm, and the other structures, parameters and preparation methods were the same as in example 1.
Example 7
A negative electrode plate was distinguished from example 1 in that the thickness of the solid electrolyte layer was 6 μm, the thickness of the active material coating was 175 μm, and the other structures, parameters and preparation methods were the same as in example 1.
Comparative example 1
A negative electrode sheet was distinguished from production example 1 only in that no solid electrolyte layer was provided, the thickness of the active material coating was 175 μm, and the other structures, parameters and production methods were the same as in production example 1.
Application example 1
A lithium ion battery comprises a positive pole piece, a negative pole piece, a composite diaphragm and electrolyte;
wherein the positive pole piece is obtained by coating positive slurry (NMC 811, carbon black and PVDF with the mass ratio of 95:5: 5) on the surface of an aluminum foil, and the single-side surface density of the positive pole piece is 40mg/cm2；
Negative electrode sheet (example 1);
composite separator (preparation example 4);
the electrolyte comprises EC, PC, EMC, VC and PS in a volume ratio of 35:5:60:1:1, and 1mol of LiPF is added6；
The preparation method of the lithium ion battery provided by the application example comprises the following steps:
(1) laminating the positive pole piece, the negative pole piece and the diaphragm in a zigzag manner (30 layers of the positive pole piece and 31 layers of the negative pole piece), and packaging with aluminum plastic to obtain an initial lithium ion battery;
(2) baking the initial lithium ion battery obtained in the step (1) at 85 ℃ for 15h, injecting electrolyte, pre-charging, aging at 45 ℃ for 72h, and forming to obtain a formed lithium ion battery;
(3) and (3) carrying out conversion on the lithium ion battery obtained in the step (2) at 45 ℃ under the current of 0.02C for 23h, and carrying out chucking at 35 ℃ under the current of 1C for 10 weeks, 30h, with the chucking pressure of 750kg, Degas and normal-temperature aging to obtain the lithium ion battery.
Application example 2
An application example 1 of a lithium ion battery is different in that the negative electrode sheet obtained in example 2 is used to replace the negative electrode sheet obtained in example 1, the composite separator obtained in preparation example 5 is used to replace the composite separator obtained in preparation example 3, and other structures, parameters and preparation methods are the same as those in application example 1.
Application example 3
An application example 1 of a lithium ion battery is different in that the negative electrode sheet obtained in example 3 is used to replace the negative electrode sheet obtained in example 1, the composite separator obtained in preparation example 6 is used to replace the composite separator obtained in preparation example 3, and other structures, parameters and preparation methods are the same as those in application example 1.
Application example 4
The difference of application example 1 of the lithium ion battery is that the negative electrode sheet obtained in example 4 is used to replace the negative electrode sheet obtained in example 1, and other structures, parameters and preparation methods are the same as those of application example 1.
Application example 5
The difference of application example 1 of the lithium ion battery is that the negative electrode sheet obtained in example 5 is used to replace the negative electrode sheet obtained in example 1, and other structures, parameters and preparation methods are the same as those of application example 1.
Application example 6
The difference of application example 1 of the lithium ion battery is that the negative electrode sheet obtained in example 6 is used to replace the negative electrode sheet obtained in example 1, and other structures, parameters and preparation methods are the same as those of application example 1.
Application example 7
The difference of application example 1 of the lithium ion battery is that the negative electrode sheet obtained in example 7 is used to replace the negative electrode sheet obtained in example 1, and other structures, parameters and preparation methods are the same as those of application example 1.
Comparative application example 1
The difference of application example 1 of the lithium ion battery is that the negative electrode sheet obtained in comparative example 1 is used to replace the negative electrode sheet obtained in example 1, and other structures, parameters and preparation methods are the same as those of application example 1.
Comparative application example 2
A lithium ion battery which is different from application example 1 only in that the production method comprises the steps of:
(1) laminating the positive pole piece, the negative pole piece and the diaphragm in a zigzag manner (30 layers of the positive pole piece and 31 layers of the negative pole piece), and packaging with aluminum plastic to obtain an initial lithium ion battery;
(2) baking the initial lithium ion battery obtained in the step (1) at 85 ℃ for 15h, injecting electrolyte, pre-charging, aging at 45 ℃ for 72h, and forming to obtain a formed lithium ion battery;
(3) and (3) carrying out pressureless formation, Degas and normal-temperature aging on the formed lithium ion battery obtained in the step (2) to obtain the lithium ion battery.
Comparative application example 3
A lithium ion battery comprises a positive pole piece, a negative pole piece, a composite diaphragm and electrolyte;
wherein the positive pole piece is obtained by coating positive slurry (NMC 811, carbon black and PVDF with the mass ratio of 95:5: 5) on the surface of an aluminum foil, and the single-side surface density of the positive pole piece is 40mg/cm2；
Negative electrode sheet (comparative example 1);
composite separator (preparation example 4);
the electrolyte comprises EC, PC, EMC, VC and PS in a volume ratio of 35:5:60:1:1, and 1mol of LiPF is added6；
The preparation method of the lithium ion battery obtained in the comparative application example comprises the following steps:
(1) laminating the positive pole piece, the negative pole piece and the diaphragm in a zigzag manner (30 layers of the positive pole piece and 31 layers of the negative pole piece), and packaging with aluminum plastic to obtain an initial lithium ion battery;
(2) baking the initial lithium ion battery obtained in the step (1) at 85 ℃ for 15h, injecting electrolyte, pre-charging, aging at 45 ℃ for 72h, and forming to obtain a formed lithium ion battery;
(3) and (3) carrying out pressureless formation, Degas and normal-temperature aging on the formed lithium ion battery obtained in the step (2) to obtain the lithium ion battery.
And (3) performance testing:
(1) and (3) observing the appearance: observing the disassembled composite diaphragm and negative electrode plate of the lithium ion battery provided in the corresponding application example 1 and the comparative application example 3 by using a scanning electron microscope (SU 8100 scanning electron microscope, Hitachi high and New technology corporation, Japan column type Co., Ltd.), wherein the test result is shown in FIGS. 2-5;
fig. 2 is a scanning electron microscope image of the negative electrode plate obtained in application example 1 after the lithium ion battery is disassembled; FIG. 3 is a scanning electron microscope image of the disassembled composite diaphragm of the lithium ion battery obtained in application example 1; as can be seen from fig. 2 and 3, the composite diaphragm provided by the present invention and the surface of the negative electrode plate form an integrated film, and a dense passivation layer is formed on both the surface of the negative electrode plate and the surface of the composite diaphragm; the compact layer is a compact passivation layer formed by the reaction of Ti atoms in LATP and Li under the electric potential close to 0V; fig. 4 is a scanning electron microscope image of a negative electrode plate obtained after a lithium ion battery is disassembled in comparative application example 3, fig. 5 is a scanning electron microscope image of a composite diaphragm obtained after the lithium ion battery is disassembled in comparative application example 3, and as can be seen from fig. 4 and fig. 5, the lithium ion battery obtained by adopting a common negative electrode plate and a traditional lithium ion battery preparation method does not have the passivation film on the surface of the diaphragm of the negative electrode plate after disassembly, so that the compact film formed by the composite diaphragm provided by the invention can prevent lithium dendrites from permeating into a base film from the positive electrode side and consume dendritic lithium, and further, safety accidents such as battery short circuit, explosion and the like caused by the fact that the lithium dendrites pierce through the lithium ion battery diaphragm are avoided.
(2) Liquid retention amount, internal resistance, 130 ℃ failure time: fully filling the lithium ion battery with a 1C constant current and a constant voltage, standing for 3h, heating the lithium ion battery in an oven at the temperature of 130 ℃, increasing the temperature from room temperature to 130 ℃ at the heating rate of 5 ℃/min, keeping the temperature at 130 ℃ for 3h, and then testing;
(3) cycle performance: the lithium ion cell was cycled at 45 ℃ to record the time at which the capacity was below 80% SOH.
(4) Energy density: energy of the first cycle of the lithium ion battery/mass of the lithium ion battery;
the lithium ion batteries obtained according to the test methods (2) and (3) in the application examples 1 to 7 and the comparative application examples 1 to 3 are tested, and the test results are shown in table 1:
TABLE 1
Figure BDA0003128623100000171
As can be seen from the data in table 1: the liquid retention capacity of the lithium ion battery prepared by the negative pole piece is 119-125 g, the internal resistance (DCR) is 1.28-1.3 m omega, the failure time is more than 2.2h at 130 ℃, the cycle performance can reach 2320-2503 weeks, and the energy density is 280-291 Wh/kg.
Compared with application example 1 and application example 1, the lithium ion battery obtained by using the negative electrode plate provided by the invention has the advantages of smaller DCR, smaller usage amount of electrolyte retention, higher energy density and more excellent cycle performance.
Comparing application example 1 with comparative application examples 2-3, it can be found that without the preparation method provided by the present invention, the obtained lithium ion battery has high internal resistance, poor cycle performance, high electrolyte retention amount, and low energy density, and the lithium ion battery with improved performance cannot be obtained.
Further comparing application examples 1 and 4-7, it can be found that when the thickness of the Ti-containing oxide solid electrolyte layer is too low (application example 6), the reduction effect on the electrolyte is weakened, and the formed passivation film is thin, so that the lithium ion battery is thermally out of control within 2.2 hours; when the thickness of the Ti-containing oxide solid electrolyte layer is too large (application example 7), the mass energy density of the lithium ion battery is reduced
In summary, for the present invention, the specific method for preparing the lithium ion battery and the specific cathode are key to improve the performance of the battery, and only under the specific process conditions of the present invention, the passivation layer can be effectively formed, thereby effectively improving the safety and cycle performance of the battery.
The applicant states that the present invention is illustrated by the above examples to a negative electrode plate and its preparation method and application, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims (10)

1. The negative pole piece is characterized by comprising a current collector, an active substance layer and a Ti-oxide-containing solid electrolyte layer which are sequentially arranged.
2. The negative electrode plate as claimed in claim 1, wherein the thickness of the negative electrode plate is 80-200 μm.
3. The negative electrode tab of claim 1 or 2, wherein the current collector comprises a copper foil;
preferably, the thickness of the active material layer is 70-190 μm;
preferably, the material of the active material coating layer includes a combination of a negative electrode active material, a conductive agent, and a binder;
preferably, the negative active material includes a silicon carbon material;
preferably, the conductive agent comprises carbon black;
preferably, the binder comprises CMC and/or SBR.
4. The negative electrode plate as claimed in any one of claims 1 to 3, wherein the thickness of the Ti oxide-containing solid electrolyte layer is 2 to 5 μm;
preferably, the raw material for preparing the Ti oxide-containing solid electrolyte layer includes a Ti oxide-containing slurry;
preferably, the Ti-containing oxide slurry comprises the following components in parts by weight: 80-95 parts by weight of Ti oxide-containing solid electrolyte, 0.5-3 parts by weight of binder and 15-70 parts by weight of solvent;
preferably, the binder comprises any one of polyvinylidene fluoride, CMC or SBR or a combination of at least two thereof;
preferably, the solvent comprises N-methylpyrrolidone;
preferably, the Ti-containing oxide includes any one of lithium titanium phosphate, lithium aluminum titanium phosphate, or lithium lanthanum titanate, or a combination of at least two thereof;
preferably, the particle size of the Ti-containing oxide is 1 to 100 nm.
5. The negative electrode sheet according to claim 4, wherein the Ti-containing oxide slurry is prepared by a method comprising the steps of:
(A1) mixing a binder and a solvent to obtain a binder glue solution;
(A2) and (D) mixing the binder glue solution obtained in the step (A1) with Ti-containing oxide to obtain the Ti-containing oxide slurry.
6. A preparation method of the negative pole piece of any one of claims 1 to 5, wherein the preparation method comprises the following steps: and sequentially coating the preparation raw material of the active substance layer and the Ti-containing oxide slurry on the surface of the current collector to obtain the negative pole piece.
7. A lithium ion battery, characterized in that the lithium ion battery comprises the negative electrode plate, the positive electrode plate, the diaphragm and the electrolyte according to any one of claims 1 to 5.
8. The method for preparing the lithium ion battery according to claim 7, wherein the method comprises the following steps:
(1) laminating and packaging the positive pole piece, the negative pole piece and the diaphragm to obtain an initial lithium ion battery;
(2) baking the initial lithium ion battery obtained in the step (1), injecting electrolyte, pre-charging, aging and forming to obtain a formed lithium ion battery;
(3) and (3) carrying out clamp formation on the formed lithium ion battery obtained in the step (2) to obtain the lithium ion battery.
9. The method according to claim 8, wherein the aging temperature in step (2) is 35-65 ℃, preferably 35-45 ℃;
preferably, the aging time of the step (2) is 70-74 h;
preferably, the method of forming the jig in step (3) comprises: the temperature is controlled to be 40-50 ℃ and the current is 0.01-0.5C, the time is 4-25h, the temperature is 30-40 ℃ and the current is 0.5-2C, the time is 10-100 h, and the clamp formation is completed;
preferably, the pressure of the clamp formed by the clamp is 50-1000 kg.
10. Use of a lithium ion battery according to claim 6 or 7 in the automotive field.
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