CN110085835A - The preparation method of anode composite material for high-energy density all-solid lithium-ion battery - Google Patents
The preparation method of anode composite material for high-energy density all-solid lithium-ion battery Download PDFInfo
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- CN110085835A CN110085835A CN201910361670.9A CN201910361670A CN110085835A CN 110085835 A CN110085835 A CN 110085835A CN 201910361670 A CN201910361670 A CN 201910361670A CN 110085835 A CN110085835 A CN 110085835A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/364—Composites as mixtures
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- 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 discloses a kind of preparation method of anode composite material for high-energy density all-solid lithium-ion battery, includes the following steps: to provide manganese acetate, lanthanum nitrate, cobalt acetate and nickel nitrate, and be dissolved in distilled water, stir, obtain salt-mixture；Salt-mixture is calcined, presoma is obtained；Presoma is mixed with lithium hydroxide, the first positive electrode component is obtained after processing；Metallic cobalt and lithium hydroxide are provided, the second positive electrode component is obtained after processing；First positive electrode component and the second positive electrode component are subjected to ball milling mixing, obtain positive electrode raw material；To the tabletting of positive electrode raw material and the first heat treatment is carried out, and carries out subzero treatment and is crushed, obtains positive electrode intermediate powder；And to the tabletting of positive electrode intermediate powder and carry out the second heat treatment.The anode composite material of high-energy density all-solid lithium-ion battery prepared by the method for the present invention can significantly improve battery performance, be conducive to industrialization promotion application.
Description
Technical field
The present invention relates to high energy-storage battery preparation technical fields, all solid state for high-energy density especially with regard to one kind
The preparation method of the anode composite material of lithium ion battery.
Background technique
Currently, with the development of new technology and new energy, intelligent mobile terminal product (such as smart phone, vehicle intelligent
Terminal, smart television, wearable device etc.) and the smart electronics product such as smart home product using more more and more universal.Especially
It is smart phone, global mobile phone user just alreadys exceed 3,000,000,000 at the beginning of 2007, with the development of the communication technology of new generation, intelligence
The market scale of mobile phone is by continuous enlargement.In face of the market of smart electronics product with rapid changepl. never-ending changes and improvements, rapid growth, as intelligent electricity
The power resources of sub- product and the battery of one of key fitment have attracted more and more attention from people and pay attention to.It is generally acknowledged that intelligence is
The summation of knowledge and intelligence, the former is intelligent basis, the ability that the latter refers to acquisition and solves with knowledge.Intelligence manufacture is answered
When comprising intelligent Manufacturing Technology and intelligent manufacturing system, intelligent manufacturing system can not only constantly enrich knowledge in practice
Library, but also there is self-learning function, there are also collection and understand environmental information and the information of itself, and analyzed and determined and advised
Draw the ability of itself behavior.It is readily apparent that the development of above-mentioned technology all be unable to do without the development of lithium ion battery.And with
The function of smart electronics product is more and more abundant, and utilization rate is higher and higher, also means that power consumption is increasing, therefore battery
Off-capacity becomes the bottleneck of entire industry development, it may be said that is the development and progress for directly limiting smart electronics product.
Solid lithium battery is divided into polymer solid lithium battery and inorganic full-solid lithium battery.For solid lithium battery
Research manufacture, lithium battery producer also strongly pursues frivolous novel light thin lithium battery.Solid lithium battery mainly includes
Anode, solid electrolyte and cathode three parts, compared with the liquid lithium ionic cell with anode, cathode, electrolyte and film,
All-solid lithium-ion battery constructively more simplifies.
For lithium ion battery, the prior art proposes a series of materials.Prior art CN106784635B discloses one
The preparation method of the kind compound cathode of lithium of solid state battery, belongs to electrochemistry and novel energy resource material technology field.The invention is mainly led to
Overheat implantation fusion method or electrodeposition process by lithium metal be deposited in three-dimensional carbon material or foam porous material void to
Compound cathode of lithium is prepared, wherein the application of three-dimensional framework plays the role of both sides, is on the one hand pre- in preparation process
Storage lithium provides sufficient space, on the other hand for circulating battery during receive lithium metal and provide carrier.Therefore, entirely
Solid state lithium battery is becoming the development trend of next-generation global lithium power technology.However in the prior art, solid lithium battery
Research all in laboratory stage, industrialization technology is also close to blank.
Prior art CN107265518B discloses a kind of lithium ion battery negative material Co with Magen David structure
(OH) F and preparation method.The material uses solvent structure, by regulating and controlling synthesis technology, can respectively obtain solid and hollow
Co (OH) F material of the Magen David structure of two kinds of different-shapes.Wherein, hollow structure can buffer the electrode material in cyclic process
In generated volume expansion, so that its be made to keep good cyclical stability.Furthermore hollow structure also helps electrolyte
Infiltration, the efficiency of transmission for increasing electrode reaction area, improving lithium ion.
Prior art CN106395765B discloses a kind of two telluride molybdenum electrochemical energy storage materials, and the material is metastable state
Two telluride molybdenums, expression formula 1T '-MoTe2, pattern be ultrathin nanometer piece assembling nanometer flower structure or nanometer spherical structure.
The present invention also provides the preparation method and application of the material, use oleyl amine for reducing agent, and hexacarbonylmolybdenum or molybdenum pentachloride are molybdenum
Predecessor, tellurium-tri octyl phosphine presoma is injected under certain temperature, by regulation reaction temperature and reaction time, to prepare
The regular two telluride molybdenum nanometer flower structure of metastable state hexagonal phase of size uniformity, shape or nano-spherical structure out.
The information disclosed in the background technology section is intended only to increase the understanding to general background of the invention, without answering
When being considered as recognizing or imply that the information constitutes the prior art already known to those of ordinary skill in the art in any form.
Summary of the invention
The purpose of the present invention is to provide a kind of anode composite materials for high-energy density all-solid lithium-ion battery
Preparation method, the shortcomings that prior art can be overcome.
To achieve the above object, it is multiple that the present invention provides a kind of anodes for high-energy density all-solid lithium-ion battery
The preparation method of condensation material, the preparation method for being used for the anode composite material of high-energy density all-solid lithium-ion battery include
Following steps:
Manganese acetate, lanthanum nitrate, cobalt acetate and nickel nitrate are provided；
Manganese acetate, lanthanum nitrate, cobalt acetate and nickel nitrate are dissolved in distilled water, precursor salt solution is obtained；
Vaporized precursor salting liquid is stirred until all distilled water evaporate, obtains salt-mixture；
Salt-mixture is calcined, presoma is obtained；
Presoma is mixed with lithium hydroxide, and carries out the first mechanical alloying processing, obtains the first positive electrode component；
Metallic cobalt and lithium hydroxide are provided；
Mixed metal cobalt and lithium hydroxide, and the second mechanical alloy is carried out to the mixture of metallic cobalt and lithium hydroxide
Change processing, obtains the second positive electrode component；
First positive electrode component and the second positive electrode component are subjected to ball milling mixing, obtain positive electrode raw material；
To the tabletting of positive electrode raw material and the first heat treatment is carried out, obtains positive electrode intermediate；
Subzero treatment is carried out to positive electrode intermediate and is crushed, positive electrode intermediate powder is obtained；And
To the tabletting of positive electrode intermediate powder and carry out second heat treatment, obtain for high-energy density all solid lithium from
The anode composite material of sub- battery.
In a preferred embodiment, the molar ratio of manganese acetate, lanthanum nitrate, cobalt acetate and nickel nitrate is 1:(1-
1.2):(1-1.05):(1-1.10)。
In a preferred embodiment, the condition of vaporized precursor salting liquid is stirred are as follows: right under mechanical agitation
Precursor salt solution is evaporated, and evaporating temperature is 80-90 DEG C, and mechanical stirring speed is 70-80rpm.
In a preferred embodiment, condition salt-mixture calcined are as follows: calcination temperature is 850-950 DEG C, is forged
The burning time is 6-9h.
In a preferred embodiment, the molar ratio of presoma and lithium hydroxide is 1:(1-1.05), carry out the first machine
Tool Alloying Treatment specifically: the mixture of presoma and lithium hydroxide is put into ball mill, drum's speed of rotation 1000-
1300rpm, Ball-milling Time 60-70h.
In a preferred embodiment, the molar ratio of metallic cobalt and lithium hydroxide is 1:(1-1.05), carry out second
Mechanical alloying specifically: the mixture of metallic cobalt and lithium hydroxide is put into ball mill, drum's speed of rotation 1300-
1500rpm, Ball-milling Time 90-100h.
In a preferred embodiment, the mass ratio of the first positive electrode component and the second positive electrode component is 1:
(0.5-0.7) carries out ball milling mixing specifically: be put into the mixture of the first positive electrode component and the second positive electrode component
Ball mill carries out ball milling, drum's speed of rotation 500-700rpm, Ball-milling Time 20-30h under an argon atmosphere.
In a preferred embodiment, the tabletting of positive electrode raw material and carry out first heat treatment specifically: to tabletting it
Positive electrode material piece afterwards carries out hot-pressing processing, and hot-pressing processing pressure is 300-400MPa, and treatment temperature is 800-900 DEG C,
The processing time is 30-40min.
In a preferred embodiment, subzero treatment is carried out to positive electrode intermediate and be crushed specifically: will be positive
Material intermediate puts into 30-40min in liquid nitrogen, then crushes the positive electrode after deep cooling.
In a preferred embodiment, to the tabletting of positive electrode intermediate powder and the second heat treatment of progress specifically:
Hot-pressing processing is carried out to the positive electrode intermediate powder after tabletting, hot-pressing processing pressure is 100-200MPa, treatment temperature
It is 1000-1050 DEG C, the processing time is 30-40min.
Compared with prior art, the anode composite material for high-energy density all-solid lithium-ion battery of the invention
Preparation method has the advantages that the present invention provides a kind of anode for high-energy density all-solid lithium-ion battery is compound
The preparation method of material.The present invention is designed by ingredient, improves battery performance, specifically, the present invention is added to La element,
Battery performance (specifically may refer to the comparison of embodiment Yu comparative example 1) is improved, bi-material layers component (the first positive electrode is passed through
Component and the second positive electrode component) design, equally improve battery performance (specifically may refer to comparative example 1 with it is existing
The comparison of technology).Material generation is carried out by mechanical alloying, avoids the process that complicated chemical method prepares material, is improved
Production efficiency has investigated a set of effective preparation process for the application system (referring specifically to comparative example 8,10,12 and real
Apply the comparison of example).By the design of subzero treatment, the principle effectively expanded with heat and contract with cold with material so that material deep cooling it
Volume contraction afterwards, internal porosity volume increase accordingly, and effectively increase crushing effect, improve the effect of the second heat treatment.Root
According to other comparative examples and embodiment not to the technical effect that can be seen that present invention design heat treatment process and cryogenic step and
Purpose.
Detailed description of the invention
Fig. 1 is the positive composite wood for high-energy density all-solid lithium-ion battery according to an embodiment of the present invention
The preparation method flow chart of material.
Specific embodiment
With reference to the accompanying drawing, specific embodiments of the present invention will be described in detail, it is to be understood that guarantor of the invention
Shield range is not limited by the specific implementation.
Unless otherwise explicitly stated, otherwise in entire disclosure and claims, term " includes " or its change
Changing such as "comprising" or " including " etc. will be understood to comprise stated element or component, and not exclude other members
Part or other component parts.
Fig. 1 is the positive composite wood for high-energy density all-solid lithium-ion battery according to an embodiment of the present invention
The preparation method flow chart of material.As shown, the anode for high-energy density all-solid lithium-ion battery of the invention is compound
The preparation method of material includes the following steps:
Step 101: manganese acetate, lanthanum nitrate, cobalt acetate and nickel nitrate are provided；
Step 102: manganese acetate, lanthanum nitrate, cobalt acetate and nickel nitrate being dissolved in distilled water, it is molten to obtain precursor salt
Liquid；
Step 103: stirring vaporized precursor salting liquid obtains salt-mixture until all distilled water evaporate；
Step 104: salt-mixture being calcined, presoma is obtained；
Step 105: presoma being mixed with lithium hydroxide, and carries out the first mechanical alloying processing, obtains the first anode
Material component；
Step 106: metallic cobalt and lithium hydroxide are provided；
Step 107: mixed metal cobalt and lithium hydroxide, and second is carried out to the mixture of metallic cobalt and lithium hydroxide
Mechanical alloying processing, obtains the second positive electrode component；
Step 108: the first positive electrode component and the second positive electrode component being subjected to ball milling mixing, obtain positive material
Expect raw material；
Step 109: to the tabletting of positive electrode raw material and carrying out the first heat treatment, obtain positive electrode intermediate；
Step 110: subzero treatment being carried out to positive electrode intermediate and is crushed, positive electrode intermediate powder is obtained；With
And
Step 111: to the tabletting of positive electrode intermediate powder and carrying out the second heat treatment, obtain complete for high-energy density
The anode composite material of solid lithium ion battery.
Embodiment 1
The preparation method of anode composite material for high-energy density all-solid lithium-ion battery includes the following steps: to mention
For manganese acetate, lanthanum nitrate, cobalt acetate and nickel nitrate；Manganese acetate, lanthanum nitrate, cobalt acetate and nickel nitrate are dissolved in distilled water
In, obtain precursor salt solution；Vaporized precursor salting liquid is stirred until all distilled water evaporate, obtains salt-mixture；It is right
Salt-mixture is calcined, and presoma is obtained；Presoma is mixed with lithium hydroxide, and carries out the first mechanical alloying processing, is obtained
To the first positive electrode component；Metallic cobalt and lithium hydroxide are provided；Mixed metal cobalt and lithium hydroxide, and to metallic cobalt with
And the mixture of lithium hydroxide carries out the second mechanical alloying processing, obtains the second positive electrode component；By the first positive electrode
Component and the second positive electrode component carry out ball milling mixing, obtain positive electrode raw material；It goes forward side by side to positive electrode raw material tabletting
Row first is heat-treated, and obtains positive electrode intermediate；Subzero treatment is carried out to positive electrode intermediate and is crushed, positive material is obtained
Expect intermediate powder；To the tabletting of positive electrode intermediate powder and the second heat treatment is carried out, is obtained entirely solid for high-energy density
The anode composite material of state lithium ion battery.Manganese acetate, lanthanum nitrate, cobalt acetate and nickel nitrate molar ratio be 1:1:1:1.It stirs
Mix the condition of vaporized precursor salting liquid are as follows: under mechanical agitation, be evaporated to precursor salt solution, evaporating temperature is
80 DEG C, mechanical stirring speed is 70rpm.The condition that salt-mixture is calcined are as follows: calcination temperature is 850 DEG C, and calcination time is
6h.The molar ratio of presoma and lithium hydroxide is 1:1, carries out the first mechanical alloying processing specifically: by presoma and hydrogen-oxygen
The mixture for changing lithium is put into ball mill, drum's speed of rotation 1000rpm, Ball-milling Time 60h.Metallic cobalt and lithium hydroxide
Molar ratio is 1:1, carries out the second mechanical alloying specifically: the mixture of metallic cobalt and lithium hydroxide is put into ball mill, ball
Mill speed is 1300rpm, Ball-milling Time 90h.The mass ratio of first positive electrode component and the second positive electrode component is
1:0.5 carries out ball milling mixing specifically: the mixture of the first positive electrode component and the second positive electrode component is put into ball milling
Machine carries out ball milling, drum's speed of rotation 500rpm, Ball-milling Time 20h under an argon atmosphere.Positive electrode raw material tabletting is gone forward side by side
Row first is heat-treated specifically: carries out hot-pressing processing to the positive electrode material piece after tabletting, hot-pressing processing pressure is
300MPa, treatment temperature are 800 DEG C, and the processing time is 30min.Subzero treatment is carried out to positive electrode intermediate and is crushed specific
Are as follows: positive electrode intermediate is put into 30min in liquid nitrogen, then crushes the positive electrode after deep cooling.To positive material
Expect intermediate powder tabletting and carry out the second heat treatment specifically: hot pressing is carried out to the positive electrode intermediate powder after tabletting
Processing, hot-pressing processing pressure are 100MPa, and treatment temperature is 1000 DEG C, and the processing time is 30min.
Embodiment 2
The preparation method of anode composite material for high-energy density all-solid lithium-ion battery includes the following steps: to mention
For manganese acetate, lanthanum nitrate, cobalt acetate and nickel nitrate；Manganese acetate, lanthanum nitrate, cobalt acetate and nickel nitrate are dissolved in distilled water
In, obtain precursor salt solution；Vaporized precursor salting liquid is stirred until all distilled water evaporate, obtains salt-mixture；It is right
Salt-mixture is calcined, and presoma is obtained；Presoma is mixed with lithium hydroxide, and carries out the first mechanical alloying processing, is obtained
To the first positive electrode component；Metallic cobalt and lithium hydroxide are provided；Mixed metal cobalt and lithium hydroxide, and to metallic cobalt with
And the mixture of lithium hydroxide carries out the second mechanical alloying processing, obtains the second positive electrode component；By the first positive electrode
Component and the second positive electrode component carry out ball milling mixing, obtain positive electrode raw material；It goes forward side by side to positive electrode raw material tabletting
Row first is heat-treated, and obtains positive electrode intermediate；Subzero treatment is carried out to positive electrode intermediate and is crushed, positive material is obtained
Expect intermediate powder；To the tabletting of positive electrode intermediate powder and the second heat treatment is carried out, is obtained entirely solid for high-energy density
The anode composite material of state lithium ion battery.Manganese acetate, lanthanum nitrate, cobalt acetate and nickel nitrate molar ratio be 1:1.2:
1.05:1.10.Stir the condition of vaporized precursor salting liquid are as follows: under mechanical agitation, steam to precursor salt solution
Hair, evaporating temperature are 90 DEG C, and mechanical stirring speed is 80rpm.The condition that salt-mixture is calcined are as follows: calcination temperature 950
DEG C, calcination time 9h.The molar ratio of presoma and lithium hydroxide is 1:1.05, and it is specific to carry out the first mechanical alloying processing
Are as follows: the mixture of presoma and lithium hydroxide is put into ball mill, drum's speed of rotation 1300rpm, Ball-milling Time 70h.Gold
The molar ratio for belonging to cobalt and lithium hydroxide is 1:1.05, carries out the second mechanical alloying specifically: by metallic cobalt and lithium hydroxide
Mixture be put into ball mill, drum's speed of rotation 1500rpm, Ball-milling Time 100h.First positive electrode component and second
The mass ratio of positive electrode component is 1:0.7, carries out ball milling mixing specifically: by the first positive electrode component and the second positive material
The mixture of material component is put into ball mill, carries out ball milling, drum's speed of rotation 700rpm under an argon atmosphere, Ball-milling Time is
30h.The tabletting of positive electrode raw material simultaneously carries out the first heat treatment specifically: carries out hot pressing to the positive electrode material piece after tabletting
Processing, hot-pressing processing pressure are 400MPa, and treatment temperature is 900 DEG C, and the processing time is 40min.To positive electrode intermediate into
Row subzero treatment is simultaneously crushed specifically: positive electrode intermediate is put into 40min in liquid nitrogen, then by the positive material after deep cooling
Material is crushed.To the tabletting of positive electrode intermediate powder and carry out the second heat treatment specifically: to the positive material after tabletting
Expect intermediate powder carry out hot-pressing processing, hot-pressing processing pressure be 200MPa, treatment temperature be 1050 DEG C, processing the time be
40min。
Embodiment 3
The preparation method of anode composite material for high-energy density all-solid lithium-ion battery includes the following steps: to mention
For manganese acetate, lanthanum nitrate, cobalt acetate and nickel nitrate；Manganese acetate, lanthanum nitrate, cobalt acetate and nickel nitrate are dissolved in distilled water
In, obtain precursor salt solution；Vaporized precursor salting liquid is stirred until all distilled water evaporate, obtains salt-mixture；It is right
Salt-mixture is calcined, and presoma is obtained；Presoma is mixed with lithium hydroxide, and carries out the first mechanical alloying processing, is obtained
To the first positive electrode component；Metallic cobalt and lithium hydroxide are provided；Mixed metal cobalt and lithium hydroxide, and to metallic cobalt with
And the mixture of lithium hydroxide carries out the second mechanical alloying processing, obtains the second positive electrode component；By the first positive electrode
Component and the second positive electrode component carry out ball milling mixing, obtain positive electrode raw material；It goes forward side by side to positive electrode raw material tabletting
Row first is heat-treated, and obtains positive electrode intermediate；Subzero treatment is carried out to positive electrode intermediate and is crushed, positive material is obtained
Expect intermediate powder；To the tabletting of positive electrode intermediate powder and the second heat treatment is carried out, is obtained entirely solid for high-energy density
The anode composite material of state lithium ion battery.Manganese acetate, lanthanum nitrate, cobalt acetate and nickel nitrate molar ratio be 1:1.1:
1.03:1.05.Stir the condition of vaporized precursor salting liquid are as follows: under mechanical agitation, steam to precursor salt solution
Hair, evaporating temperature are 85 DEG C, and mechanical stirring speed is 75rpm.The condition that salt-mixture is calcined are as follows: calcination temperature 900
DEG C, calcination time 8h.The molar ratio of presoma and lithium hydroxide is 1:1.03, and it is specific to carry out the first mechanical alloying processing
Are as follows: the mixture of presoma and lithium hydroxide is put into ball mill, drum's speed of rotation 1100rpm, Ball-milling Time 65h.Gold
The molar ratio for belonging to cobalt and lithium hydroxide is 1:1.03, carries out the second mechanical alloying specifically: by metallic cobalt and lithium hydroxide
Mixture be put into ball mill, drum's speed of rotation 1400rpm, Ball-milling Time 95h.First positive electrode component and second is just
The mass ratio of pole material component is 1:0.6, carries out ball milling mixing specifically: by the first positive electrode component and the second positive electrode
The mixture of component is put into ball mill, carries out ball milling, drum's speed of rotation 600rpm, Ball-milling Time 25h under an argon atmosphere.
The tabletting of positive electrode raw material simultaneously carries out the first heat treatment specifically: carries out at hot pressing to the positive electrode material piece after tabletting
Reason, hot-pressing processing pressure are 350MPa, and treatment temperature is 850 DEG C, and the processing time is 35min.Positive electrode intermediate is carried out
Subzero treatment is simultaneously crushed specifically: positive electrode intermediate is put into 35min in liquid nitrogen, then by the positive electrode after deep cooling
It is crushed.To the tabletting of positive electrode intermediate powder and carry out the second heat treatment specifically: to the positive electrode after tabletting
Intermediate powder carries out hot-pressing processing, and hot-pressing processing pressure is 150MPa, and treatment temperature is 1030 DEG C, and the processing time is 35min.
Comparative example 1
It is with the difference of embodiment 1: lanthanum nitrate is not added.
Comparative example 2
It is with the difference of embodiment 1: presoma is mixed and calcined with lithium hydroxide, 500 degrees Celsius of calcination temperature,
Calcination time 3h.
Comparative example 3
It is with the difference of embodiment 1: subzero treatment is not carried out to positive electrode intermediate, and directly for positive material
Material intermediate is crushed.
Comparative example 4
Be with the difference of embodiment 1: manganese acetate, lanthanum nitrate, cobalt acetate and nickel nitrate molar ratio be 1:1.3:
1.1:1.2。
Comparative example 5
It is with the difference of embodiment 1: the condition of stirring vaporized precursor salting liquid are as follows: precursor salt solution is carried out
Evaporation, evaporating temperature are 70 DEG C, are not stirred.
Comparative example 6
It is with the difference of embodiment 1: the condition that salt-mixture is calcined are as follows: calcination temperature is 800 DEG C, when calcining
Between be 5h.
Comparative example 7
Be with the difference of embodiment 1: the molar ratio of presoma and lithium hydroxide is 1:1.1.
Comparative example 8
It is with the difference of embodiment 1: carries out the first mechanical alloying processing specifically: by presoma and lithium hydroxide
Mixture be put into ball mill, drum's speed of rotation 1500rpm, Ball-milling Time 80h.
Comparative example 9
Be with the difference of embodiment 1: the molar ratio of metallic cobalt and lithium hydroxide is 1:(1-1.1).
Comparative example 10
It is with the difference of embodiment 1: carries out the second mechanical alloying specifically: by the mixed of metallic cobalt and lithium hydroxide
It closes object and is put into ball mill, drum's speed of rotation 1300-1500rpm, Ball-milling Time 90-100h.
Comparative example 11
Be with the difference of embodiment 1: the mass ratio of the first positive electrode component and the second positive electrode component is 1:
0.8。
Comparative example 12
It is with the difference of embodiment 1: carries out ball milling mixing specifically: by the first positive electrode component and the second anode
The mixture of material component is put into ball mill, carries out ball milling, drum's speed of rotation 800rpm under an argon atmosphere, and Ball-milling Time is
40h。
Comparative example 13
Be with the difference of embodiment 1: the tabletting of positive electrode raw material simultaneously carry out first heat treatment specifically: to tabletting it
Positive electrode material piece afterwards carries out hot-pressing processing, and hot-pressing processing pressure is 200MPa, and treatment temperature is 700 DEG C, handles the time
For 50min.
Comparative example 14
It is with the difference of embodiment 1: subzero treatment is carried out to positive electrode intermediate and is crushed specifically: will be positive
Material intermediate puts into 10min in liquid nitrogen, then crushes the positive electrode after deep cooling.
Comparative example 15
It is with the difference of embodiment 1: to the tabletting of positive electrode intermediate powder and carries out the second heat treatment specifically:
Hot-pressing processing is carried out to the positive electrode intermediate powder after tabletting, hot-pressing processing pressure is 300MPa, and treatment temperature is
1100 DEG C, the processing time is 50min.
It is utilized respectively the positive electrode assembled battery of embodiment 1-3 and comparative example 1-15, battery assembly method is existing
Technology, the present invention using the prior art, (" grind by the preparation of the nickelic positive electrode of all-solid lithium-ion battery core-shell structure and performance
Study carefully ", Institutes Of Technology Of Tianjin's Master dissertation, Jin Liubing) in introduce method assembled battery (2.4.1 section).To preparing
Battery testing specific discharge capacity, 200 weeks circulation after capacity retention ratio, test method is with reference also to the paper (3.4.1
Section).
Table 1
| Specific discharge capacity | Capacity retention ratio | |
| Embodiment 1 | 256 | 93% |
| Embodiment 2 | 264 | 94% |
| Embodiment 3 | 270 | 94% |
| Comparative example 1 | 235 | 90% |
| Comparative example 2 | 182 | 73% |
| Comparative example 3 | 176 | 70% |
| Comparative example 4 | 185 | 83% |
| Comparative example 5 | 169 | 85% |
| Comparative example 6 | 192 | 84% |
| Comparative example 7 | 203 | 81% |
| Comparative example 8 | 193 | 80% |
| Comparative example 9 | 184 | 76% |
| Comparative example 10 | 168 | 73% |
| Comparative example 11 | 187 | 71% |
| Comparative example 12 | 165 | 77% |
| Comparative example 13 | 178 | 76% |
| Comparative example 14 | 167 | 73% |
| Comparative example 15 | 192 | 84% |
In conclusion the present invention provides a kind of anode composite materials for high-energy density all-solid lithium-ion battery
Preparation method, the positive composite wood of high-energy density all-solid lithium-ion battery can be made using preparation method of the invention
Material, so as to significantly improve the performance of battery.The present invention is designed by ingredient, battery performance is improved, specifically, this hair
It is bright to be added to La element, battery performance is improved, by the design of bi-material layers component, equally improves battery performance.Pass through machine
Tool alloying carries out material generation, avoids the process that complicated chemical method prepares material, improves production efficiency, have investigated
A set of effective preparation process for the application system.By the design of subzero treatment, effectively expand with heat and contract with cold with material
Principle effectively increases crushing effect so that material volume contraction after deep cooling, internal porosity volume increase accordingly, and is promoted
The effect of second heat treatment, and method of the invention is conducive to the industrialization promotion application of all-solid lithium-ion battery.
The aforementioned description to specific exemplary embodiment of the invention is in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to the above instruction, can much be changed
And variation.The purpose of selecting and describing the exemplary embodiment is that explaining specific principle of the invention and its actually answering
With so that those skilled in the art can be realized and utilize a variety of different exemplary implementation schemes of the invention and
Various chooses and changes.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (10)
1. a kind of preparation method of the anode composite material for high-energy density all-solid lithium-ion battery, it is characterised in that:
The preparation method of the anode composite material for high-energy density all-solid lithium-ion battery includes the following steps:
Manganese acetate, lanthanum nitrate, cobalt acetate and nickel nitrate are provided；
The manganese acetate, lanthanum nitrate, cobalt acetate and nickel nitrate are dissolved in distilled water, precursor salt solution is obtained；
Stirring evaporates the precursor salt solution until all distilled water evaporate, and obtains salt-mixture；
The salt-mixture is calcined, presoma is obtained；
The presoma is mixed with lithium hydroxide, and carries out the first mechanical alloying processing, obtains the first positive electrode component；
Metallic cobalt and lithium hydroxide are provided；
The metallic cobalt and lithium hydroxide are mixed, and the second mechanical alloy is carried out to the mixture of metallic cobalt and lithium hydroxide
Change processing, obtains the second positive electrode component；
The first positive electrode component and the second positive electrode component are subjected to ball milling mixing, obtain positive electrode raw material；
To the positive electrode raw material tabletting and the first heat treatment is carried out, obtains positive electrode intermediate；
Subzero treatment is carried out to the positive electrode intermediate and is crushed, positive electrode intermediate powder is obtained；And
To the positive electrode intermediate powder tabletting and carry out second heat treatment, obtain for high-energy density all solid lithium from
The anode composite material of sub- battery.
2. the preparation side for the anode composite material of high-energy density all-solid lithium-ion battery as described in claim 1
Method, it is characterised in that: the manganese acetate, lanthanum nitrate, cobalt acetate and nickel nitrate molar ratio be 1:(1-1.2): (1-1.05):
(1-1.10)。
3. the preparation side for the anode composite material of high-energy density all-solid lithium-ion battery as claimed in claim 2
Method, it is characterised in that: the condition of the precursor salt solution is evaporated in stirring are as follows: under mechanical agitation, to the presoma
Salting liquid is evaporated, and evaporating temperature is 80-90 DEG C, and mechanical stirring speed is 70-80rpm.
4. the preparation side for the anode composite material of high-energy density all-solid lithium-ion battery as claimed in claim 3
Method, it is characterised in that: the condition that the salt-mixture is calcined are as follows: calcination temperature is 850-950 DEG C, calcination time 6-
9h。
5. the preparation side for the anode composite material of high-energy density all-solid lithium-ion battery as claimed in claim 4
Method, it is characterised in that: the molar ratio of the presoma and the lithium hydroxide is 1:(1-1.05), carry out the first mechanical alloying
Processing specifically: the mixture of the presoma and the lithium hydroxide is put into ball mill, drum's speed of rotation 1000-
1300rpm, Ball-milling Time 60-70h.
6. the preparation side for the anode composite material of high-energy density all-solid lithium-ion battery as claimed in claim 5
Method, it is characterised in that: the molar ratio of the metallic cobalt and the lithium hydroxide is 1:(1-1.05), carry out the second mechanical alloy
Change specifically: the mixture of the metallic cobalt and the lithium hydroxide is put into ball mill, drum's speed of rotation 1300-
1500rpm, Ball-milling Time 90-100h.
7. the preparation side for the anode composite material of high-energy density all-solid lithium-ion battery as claimed in claim 6
Method, it is characterised in that: the mass ratio of the first positive electrode component and the second positive electrode component is 1:(0.5-
0.7) ball milling mixing, is carried out specifically: by the mixture of the first positive electrode component and the second positive electrode component
It is put into ball mill, carries out ball milling, drum's speed of rotation 500-700rpm, Ball-milling Time 20-30h under an argon atmosphere.
8. the preparation side for the anode composite material of high-energy density all-solid lithium-ion battery as claimed in claim 7
Method, it is characterised in that: the positive electrode raw material tabletting simultaneously carries out the first heat treatment specifically: to the positive electrode after tabletting
Material piece carries out hot-pressing processing, and hot-pressing processing pressure is 300-400MPa, and treatment temperature is 800-900 DEG C, and the processing time is 30-
40min。
9. the preparation side for the anode composite material of high-energy density all-solid lithium-ion battery as claimed in claim 8
Method, it is characterised in that: subzero treatment is carried out to the positive electrode intermediate and is crushed specifically: among the positive electrode
Body puts into 30-40min in liquid nitrogen, then crushes the positive electrode after deep cooling.
10. the preparation side for the anode composite material of high-energy density all-solid lithium-ion battery as claimed in claim 9
Method, it is characterised in that: to the positive electrode intermediate powder tabletting and carry out the second heat treatment specifically: after tabletting
Positive electrode intermediate powder carries out hot-pressing processing, and hot-pressing processing pressure is 100-200MPa, treatment temperature 1000-1050
DEG C, the processing time is 30-40min.
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