CN111370674A - Low-expansion metal lithium negative electrode, preparation method thereof and lithium battery - Google Patents

Low-expansion metal lithium negative electrode, preparation method thereof and lithium battery Download PDF

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Publication number
CN111370674A
CN111370674A CN202010210998.3A CN202010210998A CN111370674A CN 111370674 A CN111370674 A CN 111370674A CN 202010210998 A CN202010210998 A CN 202010210998A CN 111370674 A CN111370674 A CN 111370674A
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China
Prior art keywords
lithium metal
lithium
porous alumina
negative electrode
low
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Pending
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CN202010210998.3A
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Chinese (zh)
Inventor
王成豪
李正林
翁星星
陈朝晖
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Jiangsu Housheng New Energy Technology Co Ltd
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Jiangsu Housheng New Energy Technology Co Ltd
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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
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of lithium batteries, and particularly relates to a low-expansion metal lithium cathode, a preparation method thereof and a lithium battery. The low-expansion metal lithium negative electrode comprises the following raw materials: lithium metal, porous alumina, a conductive agent; and the mass ratio of the three is 1: (3-10): (0.005-0.3). In the charging process, the porous alumina provides a framework space of the low-expansion metal lithium cathode, so that the cathode is ensured to be almost not expanded integrally, and the service life of the battery is further prolonged.

Description

Low-expansion metal lithium negative electrode, preparation method thereof and lithium battery
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a low-expansion metal lithium cathode, a preparation method thereof and a lithium battery.
Background
In a conventional lithium metal battery, lithium metal is used as a negative electrode, and during charging and discharging, because no framework is used for supporting, the volume expansion of the lithium metal is large during charging, and the service life of the battery is shortened.
Disclosure of Invention
The invention provides a low-expansion metal lithium negative electrode, a preparation method thereof and a lithium battery.
In order to solve the technical problem, the invention provides a lithium metal negative electrode, which comprises the following raw materials: lithium metal, porous alumina, a conductive agent; and the mass ratio of the three is 1: (3-10): (0.005-0.3).
In a second aspect, the present invention provides a method for preparing a lithium metal anode, comprising the steps of: step S1, melting the lithium metal; step S2, doping porous alumina to enable lithium metal to enter internal gaps of the porous alumina; step S3, adding a conductive agent; and step S4, stirring uniformly.
In a third aspect, the present invention provides a lithium battery comprising: a negative electrode; the negative electrode employs the metallic lithium negative electrode as described above.
The low-expansion metallic lithium cathode and the preparation method thereof have the advantages that the lithium battery is prepared by mixing the lithium metal, the porous alumina, the conductive agent and the like serving as raw materials, the lithium metal is doped with the porous alumina in a molten state, the lithium metal enters the internal gap of the alumina under the capillary action of the alumina, and the skeleton space provided by the porous alumina ensures that the lithium metal cathode is hardly expanded in the charging process, so that the service life of the battery is prolonged.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a flow chart of a process for making a lithium metal anode of the present invention;
fig. 2 is a graph comparing the expansion rates of the lithium battery of the present invention and the conventional lithium metal battery.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A first part:
in view of the fact that conventional lithium metal batteries are not supported by a framework and have large volume expansion in the charging process, which causes the reduction of the service life of the batteries, the invention provides a low-expansion metal lithium cathode, which comprises the following raw materials: lithium metal, porous alumina, a conductive agent; and the mass ratio of the three is 1: (3-10): (0.005-0.3). The porous alumina is doped in the molten state of the lithium metal, so that the lithium metal enters the internal gap of the alumina under the capillary action of the alumina, and in the charging process, the porous alumina provides a skeleton space of the low-expansion metal lithium cathode, so that the cathode is ensured to be almost not expanded, and the service life of the battery is prolonged. In addition, by regulating the proportion of the lithium metal and the porous alumina, the proportion of the lithium metal occupying the internal voids of the porous alumina is 1/5-1/2, and can be selected from 1/4 and 1/3. If the ratio is too high, the internal voids of the porous alumina do not provide sufficient expansion space for the metallic lithium, and the metallic lithium of the negative electrode expands too much, and if the ratio is too low, the active lithium content of the negative electrode is too low, and the energy density of the battery is reduced.
Optionally, the mass ratio of the lithium metal, the porous alumina and the conductive agent is 1: 5.6: 0.04.
optionally, the mass ratio of the lithium metal, the porous alumina and the conductive agent is 1: 8: 0.1.
optionally, the conductive agent comprises carbon nanotubes. The carbon nano-tube has small particle size and uniform particle size distribution, and can ensure that the doped cathode has better uniformity, thereby ensuring the stability of the battery; in addition, the carbon nano tube has large specific surface area, can achieve good performance only by a small amount, can improve the content of active lithium, and improves the energy density of the battery.
As an alternative embodiment of porous alumina.
The particle size D50 of the porous alumina is 0.1-5.0 μm, and D50 can be 0.6 μm or 3 μm; and the pore volume of the internal void is 0.5-10ml/g, optionally 1.2ml/g, 3.6ml/g, 6.8 ml/g. The requirement of the particle size range is mainly because the uniformity is poor when the particle size is too large, and the pore volume cannot be sufficiently large when the particle size is too small; the too high pore volume of the alumina can cause the structural strength of the alumina to be reduced and the structure to be easily collapsed; whereas a low pore volume does not accommodate enough active lithium. Therefore, the particle size and the pore volume of the porous alumina are required to meet the application requirements, such as the porous alumina with the particle size of D50=0.8 μm and the pore volume of 1.0 ml/g; porous alumina with a particle size D50=2.0 μm and a pore volume of 3.0 ml/g; porous alumina with a particle size D50=4.0 μm and a pore volume of 5.0 ml/g.
Further, referring to fig. 1, the present invention provides a method for preparing a lithium metal anode, comprising the steps of: step S1, melting the lithium metal; step S2, doping porous alumina to enable lithium metal to enter internal gaps of the porous alumina; step S3, adding a conductive agent; and step S4, stirring uniformly to obtain the lithium metal negative electrode. Specifically, the molten lithium metal is mixed with the porous alumina, and the molten lithium metal can be doped into the porous alumina or added into the porous alumina. However, since lithium metal is in a molten state and is not easy to handle, it is preferable to dope porous alumina into the molten lithium metal.
Optionally, the above steps are all performed in a vacuum environment. Because the lithium metal can produce violent chemical reaction when it is in contact with water, so that it can produce fire and explosion, and the action of vacuum is mainly that the lithium metal can be reacted with substances of water and oxygen in the air.
In a third aspect, the present invention provides a lithium battery comprising: a negative electrode; the negative electrode employs the metallic lithium negative electrode as described above.
A second part:
example 1
Melting 10kg of a lithium metal negative electrode in a vacuum environment;
40kg of porous alumina having a pore volume of 5 ml/g and a particle diameter D50 of 3 μm was doped into a molten lithium metal negative electrode, and mechanical stirring was performed in a vacuum environment;
then 0.1kg of carbon nano tube conductive agent is added, and mechanical stirring is carried out in a vacuum environment;
stirring for a certain time to prepare the low-expansion metallic lithium cathode.
Example 2
Melting 10kg of a lithium metal negative electrode in a vacuum environment;
30kg of porous alumina having a pore volume of 0.5 ml/g and a particle diameter D50 of 0.1 μm was doped into a molten lithium metal negative electrode, and mechanical stirring was performed in a vacuum environment;
then 30kg of carbon nano tube conductive agent is added, and mechanical stirring is carried out in a vacuum environment;
stirring for a certain time to prepare the low-expansion metallic lithium cathode.
Example 3
Melting 10kg of a lithium metal negative electrode in a vacuum environment;
the method comprises the following steps of (1) doping 100kg of porous alumina with the pore volume of 10ml/g and the particle size D50 of 2 mu m into a molten lithium metal negative electrode, and mechanically stirring in a vacuum environment;
then 10kg of carbon nano tube conductive agent is added, and mechanical stirring is carried out in a vacuum environment;
stirring for a certain time to prepare the low-expansion metallic lithium cathode.
Example 4
Melting 10kg of a lithium metal negative electrode in a vacuum environment;
30kg of porous alumina having a pore volume of 0.5 ml/g and a particle diameter D50 of 0.1 μm was doped into a molten lithium metal negative electrode, and mechanical stirring was performed in a vacuum environment;
then adding 1kg of carbon nano tube conductive agent, and mechanically stirring in a vacuum environment;
stirring for a certain time to prepare the low-expansion metallic lithium cathode.
Example 5
Melting 10kg of a lithium metal negative electrode in a vacuum environment;
60kg of porous alumina having a pore volume of 2ml/g and a particle diameter D50 of 0.5 μm was doped into a molten lithium metal negative electrode, and mechanical stirring was performed in a vacuum environment;
then 0.05kg of carbon nano tube conductive agent is added, and mechanical stirring is carried out in a vacuum environment;
stirring for a certain time to prepare the low-expansion metallic lithium cathode.
Example 6
In this example 6, the lithium battery prepared in example 1 and the conventional lithium metal battery were respectively subjected to the negative electrode expansion rate test, and the test results are shown in fig. 2. The lithium battery of the invention (corresponding to the new model in fig. 2) has a negative electrode expansion of 2%, while the conventional lithium metal (corresponding to the conventional one in fig. 2) has a negative electrode expansion of 40%; therefore, the lithium metal is doped with the porous alumina in a molten state, the lithium metal enters the internal gap of the alumina under the capillary action of the alumina, and the lithium metal cathode can ensure almost no expansion through the framework space provided by the porous alumina in the charging process, so that the service life of the battery is prolonged.
In summary, according to the low-expansion metallic lithium negative electrode and the preparation method thereof, the lithium battery is prepared by mixing the lithium metal, the porous alumina, the conductive agent and the like as raw materials, the lithium metal is doped with the porous alumina in a molten state, the lithium metal enters the internal gaps of the alumina under the capillary action of the alumina, and the ratio of the lithium metal to the porous alumina is regulated, so that the lithium metal occupies the internal gaps of the porous alumina at a ratio of 1/5-1/2, and the porous alumina can provide enough framework space to ensure that the lithium metal negative electrode is hardly expanded in the charging process, thereby prolonging the service life of the battery.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (9)

1. A lithium metal anode is characterized by comprising the following raw materials:
lithium metal, porous alumina, a conductive agent; and
the mass ratio of the three components is 1: (3-10): (0.005-0.3).
2. The lithium metal anode according to claim 1,
the grain diameter D50 of the porous alumina is 0.1-5.0 μm, and the pore volume of the internal space is 0.5-10 ml/g.
3. The lithium metal anode according to claim 1,
the lithium metal occupies the porous alumina at an internal void fraction of 1/5 to 1/2.
4. The lithium metal anode according to claim 1,
the conductive agent includes carbon nanotubes.
5. A preparation method of a lithium metal negative electrode is characterized by comprising the following steps:
step S1, melting the lithium metal;
step S2, doping porous alumina to enable lithium metal to enter internal gaps of the porous alumina;
step S3, adding a conductive agent; and
and step S4, stirring uniformly.
6. The production method according to claim 5,
the grain diameter D50 of the porous alumina is 0.1-5.0 μm, and the pore volume of the internal space is 0.5-10 ml/g.
7. The production method according to claim 5,
the lithium metal occupies the porous alumina at an internal void fraction of 1/5 to 1/2.
8. The production method according to claim 5,
each step is carried out in a vacuum environment.
9. A lithium battery, comprising:
a negative electrode;
the negative electrode uses the lithium metal negative electrode according to claim 1.
CN202010210998.3A 2020-03-24 2020-03-24 Low-expansion metal lithium negative electrode, preparation method thereof and lithium battery Pending CN111370674A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015021368A1 (en) * 2013-08-09 2015-02-12 Robert Bosch Gmbh Li-ion battery with alumina coated porous silicon anode
CN105185938A (en) * 2015-07-21 2015-12-23 大连比克动力电池有限公司 Anode of lithium-ion battery and lithium-ion battery prepared from same
CN106252651A (en) * 2016-11-01 2016-12-21 深圳市贝特瑞新能源材料股份有限公司 A kind of lithium ion battery porous composite negative pole material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015021368A1 (en) * 2013-08-09 2015-02-12 Robert Bosch Gmbh Li-ion battery with alumina coated porous silicon anode
CN105185938A (en) * 2015-07-21 2015-12-23 大连比克动力电池有限公司 Anode of lithium-ion battery and lithium-ion battery prepared from same
CN106252651A (en) * 2016-11-01 2016-12-21 深圳市贝特瑞新能源材料股份有限公司 A kind of lithium ion battery porous composite negative pole material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FENG GUO等: "A Li-dual carbon composite as stable anode material for Li batteries", 《ENERGY STORAGE MATERIALS》 *
LEI FAN等: "Enabling Stable Lithium Metal Anode via 3D Inorganic Skeleton with Superlithiophilic Interphase", 《ADVANCED ENERGY MATERIALS》 *

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Application publication date: 20200703