CN114506833A - Lithium battery positive electrode material and preparation method thereof - Google Patents

Lithium battery positive electrode material and preparation method thereof Download PDF

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CN114506833A
CN114506833A CN202210089620.1A CN202210089620A CN114506833A CN 114506833 A CN114506833 A CN 114506833A CN 202210089620 A CN202210089620 A CN 202210089620A CN 114506833 A CN114506833 A CN 114506833A
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reaction kettle
positive electrode
slurry
electrode material
carbon
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CN114506833B (en
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徐荣益
李亨利
孔令涌
李意能
刘其峰
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Shenzhen Dynanonic Co ltd
Foshan Dynanonic Technology Co ltd
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Foshan Dynanonic Technology Co ltd
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Abstract

The invention belongs to the technical field of lithium battery materials, and particularly discloses a lithium battery positive electrode material and a preparation method thereof. The lithium battery anode material is prepared by adopting a reaction kettle with a carbon material three-dimensional grid. The lithium battery anode material provided by the invention has a plurality of long-range orderly through-communicated pore channels inside the anode material. By directionally constructing long-range ordered pore channels in the positive electrode material, the electrochemical performance of the battery at low temperature can be improved.

Description

Lithium battery positive electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium battery materials, and particularly relates to a lithium battery positive electrode material and a preparation method thereof.
Background
LiFePO4The raw material of the anode material has wide source, no environmental pollution, good safety performance and long cycle lifeThe lithium ion battery anode material has the advantages of being long and the like, so that the lithium ion battery anode material is unique in a plurality of lithium ion battery anode materials and is considered as one of the lithium ion battery anode materials with great potential. Using LiFePO4The prepared lithium ion battery has high safety performance, is suitable for being used as a power battery, and has good medium-rate cycle performance and cycle life of thousands of times.
However, LiFePO4Lithium ion batteries as power batteries have poor low temperature performance, which affects LiFePO4The lithium ion battery is applied to a low-temperature special environment. The analysis shows that LiFePO4The low-temperature performance of the battery is mainly related to the conductivity of electrolyte at low temperature, the interface performance of electrodes and Li in the positive electrode material of the battery+Is relevant. Wherein the electrolyte is LiFePO4Slow charge transfer at the/C interface and Li+In LiFePO4The diffusion capability of the body is an important factor affecting the low temperature performance of the battery.
Currently improved LiFePO4The research on the low-temperature performance of the cathode material has been reported in a large number, and methods for improving the low-temperature performance of the material are proposed. For example: (1) high-valence ions or metal oxides are doped to increase the intrinsic conductivity of the material; (2) reducing particle size and shortening Li+The diffusion distance of (d); (3) coated with carbon or on LiFePO4The surface of the material is coated with other conductive substances, so that the surface conductivity of the material is increased. However, these improved techniques have not resulted in LiFePO4The battery can meet the requirements of practical application at low temperature.
The poor low-temperature performance has become a main reason for limiting the application of the lithium iron phosphate battery in the field of electric automobiles, special fields and extreme environments, so that the development of the lithium ion battery with excellent low-temperature performance is an urgent need in the current market.
Disclosure of Invention
The invention mainly solves the technical problem of providing a lithium battery anode material and a preparation method of the lithium battery anode material. According to the invention, the long-range ordered through center and through communicated pore canal is directionally constructed in the positive electrode material, so that the electrochemical performance of the battery at low temperature is improved.
In order to solve the technical problems, the invention adopts the following technical scheme.
In a first aspect, the invention provides a lithium battery positive electrode material, wherein a plurality of long-range orderly through-communicated pore channels are formed in the positive electrode material.
Preferably, the pore diameter of the pore channel is 3-50 nm.
The pore space of the pore channels is 20-500 nm.
In a preferred embodiment of the present invention, the lithium battery positive electrode material is a phosphate-based positive electrode material. More preferably, a lithium iron phosphate or lithium manganese iron phosphate positive electrode material, and still more preferably a lithium manganese iron phosphate positive electrode material.
In a second aspect, the invention provides a preparation method of a lithium battery cathode material, wherein the cathode material is prepared by adopting a reaction kettle with a carbon material three-dimensional grid.
Preferably, the reaction kettle with the carbon material three-dimensional grid comprises an outer shell, a lining barrel is arranged in the outer shell, the lining barrel is internally provided with the three-dimensional grid formed by interweaving a plurality of carbon fiber yarns, and the periphery of the three-dimensional grid is connected with the inner wall of the lining barrel.
Further preferably, the diameter of the carbon fiber filament is 3-50 nm.
The space between adjacent carbon fiber filaments in the same grid layer of the three-dimensional grid of the carbon material is 20-500 nm, and the space between adjacent grid layers is 20-500 nm.
Preferably, the carbon fiber yarn raw material is subjected to acidification treatment by strong oxidizing acid, and the strong oxidizing acid is preferably nitric acid or concentrated sulfuric acid.
As a preferred embodiment of the present invention, the preparation method comprises the steps of: filling slurry of a precursor of a positive electrode material into the reaction kettle with the carbon material three-dimensional grid, and stopping filling the slurry when the liquid level in the reaction kettle reaches a set height; and then roasting the mixture in an inert atmosphere to obtain the lithium battery positive electrode material.
Further preferably, the reation kettle with the three-dimensional net of carbon material the shell body with interior bushing rotating fit sets up, the sample inlet has been seted up on the lateral wall of interior bushing, it is provided with the transfusion hole to correspond the cooperation on reation kettle's the shell body, interior bushing rotates the in-process and has the messenger the sample inlet with transfusion hole intercommunication complex first station and messenger the sample inlet by the second station of reation kettle's shell body shutoff.
The step of filling the slurry of the precursor of the cathode material into the reaction kettle with the three-dimensional grid of the carbon material by adopting the reaction kettle with the three-dimensional grid of the carbon material comprises the following steps: and rotating the lining cylinder to a first station, injecting the slurry into the reaction kettle from the side part of the reaction kettle through the infusion hole and the sample injection hole in sequence, rotating the lining cylinder to a second station after the liquid level of the slurry injected into the reaction kettle reaches a set height, and finishing slurry filling.
More preferably, the slurry in the reaction kettle is injected into the reaction kettle from the side part of the reaction kettle, and simultaneously, the slurry is injected into the reaction kettle from the top part of the reaction kettle. Namely, the slurry is filled into the reaction kettle with the carbon material three-dimensional grid, and the slurry is filled in the reaction kettle by simultaneously injecting from the side part of the reaction kettle and injecting from the top part of the reaction kettle.
As a preferred embodiment of the invention, after the filling is finished, the roasting temperature is 300-700 ℃; the preferable roasting time is 8-20 h.
As a preferred embodiment of the present invention, the ratio of the precursor to water in the slurry of the precursor of the positive electrode material is: the amount of water is 60-200% of the mass of the precursor of the positive electrode material.
Preferably, the slurry is prepared by mixing the positive electrode material precursor with water, sanding and then sieving, and preferably, the sieved sieve is more than or equal to 2000 meshes. The prepared slurry is fine and uniform and has good filling effect.
As a preferred embodiment of the present invention, the method for preparing the positive electrode material comprises the steps of:
filling slurry of a precursor of a positive electrode material into the reaction kettle with the carbon material three-dimensional grid, and stopping filling the slurry when the liquid level of the slurry in the reaction kettle reaches a set height;
roasting the reaction kettle in an inert atmosphere;
and taking out the roasted product from the reaction kettle, mixing the roasted product with a carbon source, and roasting for the second time to obtain the lithium battery cathode material.
The preparation method comprises two times of roasting, preferably, the roasting temperature is 300-500 ℃ in an inert atmosphere.
Or, the preparation method of the cathode material comprises the following steps:
filling slurry of the precursor of the anode material mixed with the carbon source into the reaction kettle with the carbon material grid until the liquid level of the slurry in the reaction kettle is slightly lower than the top surface of the three-dimensional grid, and stopping filling the slurry;
roasting the reaction kettle in an inert atmosphere;
and taking out the roasted product from the reaction kettle to obtain the lithium battery cathode material.
The preparation method comprises one-time roasting, preferably, the roasting temperature is 500-700 ℃ in an inert atmosphere.
Preferably, the carbon source is any one or a mixture of glucose, sucrose, PVDF, carbon black, PEG, and paraffin.
According to the preparation method provided by the invention, the precursor slurry of the anode material is injected into a reaction kettle with a carbon material three-dimensional grid, the slurry is filled into the reaction kettle until the liquid level of the slurry is slightly lower than the three-dimensional grid, the slurry and the three-dimensional grid are wrapped, then the anode material of the lithium battery is prepared through roasting treatment, and long-range ordered pore canals are directionally constructed and formed in the anode material, so that the electrochemical performance of the battery at low temperature can be improved.
Further, the carbon material for preparing the three-dimensional grid of the carbon material is subjected to acidification treatment in strong oxidizing acid, wherein the strong oxidizing acid can be nitric acid or sulfuric acid and the like. Through acid treatment of strong oxidizing acid, water-absorbing functional groups such as hydroxyl, carboxyl and the like are introduced to the surface of the carbon raw material, so that the affinity effect of a precursor of the positive electrode material and the carbon fiber filament can be promoted, the carbon fiber filament can be more easily used as an attachment point for forming crystal nuclei, crystals grow around the carbon fiber filament, a pore channel penetrating through the center of the crystals is left in the crystals through a subsequent roasting process, and lithium ions which are difficult to migrate in the center of the crystals can be more easily migrated outwards. And the designed range of the space between the hydrophilic carbon fiber filaments is wider.
According to the lithium battery anode material provided by the invention, the long-range orderly and mutually communicated through-channels are directionally constructed through penetrating the center and manganese doping is combined, namely, on the basis of manganese ion doping, the long-range orderly and communicated through-channel structure penetrating the center is directionally constructed in the anode material, so that the Li at low temperature can be greatly improved+The electron transfer rate plays a great role in promoting the improvement of the low-temperature performance of the battery, and the low-temperature electrochemical performance of the battery is obviously improved; can reduce the low-temperature impedance of the anode material and realize the purpose of excellent electrochemical performance of the battery at low temperature.
According to the preparation method of the lithium battery cathode material, in the preparation process, through design of a three-dimensional grid structure of the carbon material, such as through design of the cross section shape and size of the carbon fiber filaments, the cathode material with through-holes with different shapes and different apertures inside is prepared, or through design of the distribution density of the carbon fiber filaments in the three-dimensional grid, long-range ordered holes with different hole distribution are constructed in the cathode material crystal. The preparation method has the advantages of flexibility, simplicity and easy control.
Drawings
FIG. 1 is a schematic structural view of a slurry filling apparatus used in an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a reaction kettle with a three-dimensional grid of carbon material;
FIG. 3 is an XRD characterization pattern of the positive electrode materials respectively prepared in example 3 of the present invention and comparative example 1;
FIG. 4 is a TEM representation of the positive electrode material prepared in example 3 of the present invention;
FIG. 5 is a TEM representation of a positive electrode material prepared in comparative example 1 of the present invention;
fig. 6 is a buckle electric characterization map of the buckle lithium ion battery prepared by the application example of the invention.
Detailed Description
The technical solution of the present invention will be described in detail by specific examples.
Some specific embodiments of the present invention are given below. It should be specifically noted that the following examples are only representative of a portion of the many examples, and that modifications and optimizations made by those skilled in the art to the method for measuring phosphorus content by a potentiometric titrator without departing from the spirit of the present invention are considered to be within the scope of the present patent.
The cathode material in the invention is preferably a lithium iron manganese phosphate cathode active material. The precursor of the positive electrode material is prepared from a lithium source, an iron source, a phosphorus source and a manganese source; further, the positive electrode material precursor is prepared by adopting a liquid phase method.
Preferably, the lithium source is Li2CO3、LiH2PO4、LiOH·H2Any one or a mixture of more of O; the iron source is Fe (NO)3)3、Fe2O3、FeSO4·7H2Any one or a mixture of more of O; the phosphorus source is (NH)4)3PO4、LiH2PO4、H3PO4Any one or a mixture of several of them; the manganese source is MnO2、Mn(NO3)2、MnSO4、Mn3(PO4)2·3H2Any one or a mixture of several kinds of O.
In the present invention, the reaction kettle structure with the carbon material three-dimensional grid is preferably adopted as follows:
-an outer shell 1 comprising a reaction vessel;
and an inner liner 2 disposed inside said outer shell 1 with a running fit;
a three-dimensional grid 3 formed by interweaving a plurality of carbon fiber yarns is arranged in the lining cylinder 2, and the periphery of the three-dimensional grid 3 is connected with the inner wall of the lining cylinder.
As a specific implementation mode, a sample inlet hole 7 is formed in the side wall of the lining barrel 2, and a transfusion hole 6 is correspondingly and cooperatively formed in the outer shell 1 of the reaction kettle. The inner lining barrel 2 is provided with a first station for communicating and matching the sample inlet 7 with the infusion hole 6 and a second station for plugging the sample inlet 7 by the reaction kettle outer shell 1 in the rotating process.
During a first station, the sample inlet hole 7 formed in the side wall of the inner lining barrel 2 is communicated and matched with the infusion hole 6 formed in the side wall of the reaction kettle shell 1, at the moment, the slurry can be input into the inner lining barrel 2 of the reaction kettle from the reaction kettle through the infusion hole 6 and the sample inlet hole 7 in sequence, and the slurry enters the inner lining barrel 2 and is in contact with the three-dimensional grid of the carbon material.
When the slurry enters the inner lining barrel 2 and the liquid level of the slurry injected into the reaction kettle is not higher than the top surface of the carbon material three-dimensional grid 3, the inner lining barrel 2 can be rotated to a second station, so that the sample injection hole 7 is blocked by the reaction kettle outer shell 1, and after the reaction kettle slurry is completely filled, heating and roasting treatment are started.
Preferably, the injecting the slurry into the reaction kettle with the carbon material three-dimensional grid comprises the following steps: rotating the lining barrel 2 to a first station, injecting the slurry into the lining barrel 2 of the reaction kettle from the side part of the reaction kettle through the infusion hole 6 and the sample inlet hole 7 in sequence, and injecting the slurry into the lining barrel 2 of the reaction kettle from the top part of the reaction kettle; and when the liquid level of the slurry injected into the reaction kettle is not higher than the top surface of the carbon material three-dimensional grid 3, rotating the lining cylinder to a second station, and finishing slurry filling.
Preferably, the inner wall of the reaction kettle outer shell 1 is a cylinder, the lining cylinder 2 is also a cylinder, and the lining cylinder 2 and the reaction kettle outer shell 1 are installed in a rotating and matching manner.
Preferably, the side wall of the inner liner 2 is provided with at least one sampling hole 7, and preferably two sampling holes 7. And a corresponding transfusion hole 6 is formed in the side wall of the reaction kettle outer shell 1.
Preferably, the slurry is fed by a metering pump under pressure, and is pumped from two infusion holes 6 in the side wall of the outer shell 1 of the reaction kettle and is matched with the spraying mode at the top of the reaction kettle to fill the inner cavity of the lining cylinder 2. By adopting the filling mode, the filling gaps can be reduced, the generation of filling bubbles is avoided, and the performance of the prepared cathode material is ensured.
Further preferably, the outer shell of the reaction kettle is made of a high-temperature-resistant metal material.
The lining cylinder 2 and the carbon material three-dimensional grid 3 arranged in the lining cylinder are integrally arranged or separately arranged.
For example, the liner 2 may be formed by printing a carbon material integrally with the three-dimensional carbon mesh 3 provided inside by a 3D printing method. The carbon material three-dimensional grid 3 is formed by mutually connecting carbon fiber wires to form a network structure.
And after the anode material slurry is filled in the reaction kettle, roasting, wherein the roasting treatment is to heat the reaction kettle in an inert atmosphere, raise the temperature to 300-700 ℃, and keep the constant temperature for 8-20 h.
The method for preparing the lithium battery anode material can adopt a one-time roasting method or a two-time roasting method, and both use a reaction kettle with a carbon material three-dimensional grid.
Wherein, the steps of the primary roasting method comprise:
(1) taking a lithium source, an iron source, a phosphorus source and a manganese source, and preparing the precursor of the positive electrode material by adopting a liquid phase method.
(2) Adding a proper amount of water into the precursor of the positive electrode material, uniformly mixing with a carbon source, sanding and screening to obtain filtrate, namely the prepared slurry.
(3) The slurry is pumped into the lining cylinder from the side wall and/or the upper part of the reaction kettle by a metering pump.
(4) After the slurry is filled, rotating the lining cylinder, and cutting off the communication state between the lining cylinder and the shell hole of the reaction kettle; and (3) placing the reaction kettle in a tubular furnace in an inert atmosphere, and roasting.
(5) And after roasting is finished, taking out the sample from the reaction kettle, and crushing and sieving to obtain the active component of the anode material with a plurality of long-range orderly through communicated pore channels in the crystal.
The preparation method comprises the step of roasting once, and preferably, the roasting temperature is 500-700 ℃ in an inert atmosphere.
The steps of the double roasting method comprise:
(1) taking a lithium source, an iron source, a phosphorus source and a manganese source, and preparing the precursor of the positive electrode material by adopting a liquid phase method.
(2) Adding a proper amount of water into the precursor of the positive electrode material, uniformly mixing, sanding and passing through a screen; the filtrate is the prepared slurry.
(3) The slurry is pumped into the lining cylinder from the side wall and the upper part of the reaction kettle by a metering pump.
(4) After the slurry is filled, rotating the lining cylinder, and cutting off the communication state between the lining cylinder and the shell hole of the reaction kettle; and (3) placing the reaction kettle in a tubular furnace in an inert atmosphere, and roasting.
(5) After the calcination, the sample is taken out of the reaction kettle, crushed and sieved.
(6) Then, the mixture is evenly mixed with a carbon source and is roasted for the second time in an inert atmosphere. And crushing and sieving the sample to obtain the active component of the anode material with regular pore channels in the crystal.
The preparation method comprises two times of roasting, and preferably, the roasting temperature is 300-500 ℃ in an inert atmosphere.
During secondary roasting, the temperature is preferably kept constant at 600-800 ℃ for 12-30 hours.
The technical scheme of the present invention will be described in detail below by way of specific examples, wherein the reagents used therein are all commercially available. Wherein the percentages are mass percentages.
Example 1
The embodiment provides a preparation method of a lithium battery positive electrode material, which comprises the following steps:
(1) 148.68g of Li were taken2CO3、224.93g Fe2O3、600g(NH4)3PO4、104.96gMnO2Dissolving in solution containing complexing agent, mixing, and preparing LiMn by liquid phase method0.3Fe0.7PO4And (3) precursor.
The complexing agent may be one or more of citric acid, tartaric acid, succinic acid, oxalic acid, sulfosalicylic acid and lactic acid, and citric acid is used in this embodiment.
(2) Mixing LiMn0.3Fe0.7PO4The precursor is added into water and uniformly mixed, and the proportion of the precursor to the water is as follows: the amount of water is the precursor constitution100% of the amount; and then sanding, and screening by a 3000-mesh screen to obtain filtrate, namely the slurry.
(3) The filtrate was pumped into a reaction vessel having a three-dimensional grid of a carbon material by a metering pump at a rate of 1 mL/min.
The schematic structural diagram of the slurry filling apparatus used in this example is shown in fig. 1, and the structure of the reaction vessel having a three-dimensional grid of carbon material is shown in fig. 2.
As shown in fig. 1 and 2, the reactor having the carbon material three-dimensional grid includes a reactor outer shell 1 and a liner 2 rotatably disposed in the reactor outer shell 1, and the carbon material three-dimensional grid 3 is disposed in the liner 2. The lateral wall of the lining barrel 2 is provided with a sample inlet hole 7, the lateral wall of the reaction kettle shell 1 is correspondingly provided with a transfusion hole 6, the sample inlet hole 7 is matched with the transfusion hole 6, and the lining barrel 2 is provided with a first station for communicating and matching the sample inlet hole 7 with the transfusion hole 6 and a second station for plugging the sample inlet hole 7 by the reaction kettle shell 1 in the rotation process.
During a first station, a sample inlet hole 7 formed in the inner lining cylinder 2 is communicated and matched with a transfusion hole 6 formed in the reaction kettle outer shell 1, at the moment, slurry can be input into the reaction kettle from the outside of the reaction kettle through the transfusion hole 6 and the sample inlet hole 7 in sequence, and the slurry enters the inner lining cylinder 2 and contacts with the carbon material three-dimensional grid 3. When the slurry enters the inner lining barrel 2, the liquid level of the slurry injected into the reaction kettle is slightly lower than the top surface of the carbon material three-dimensional grid 3 and the liquid level does not descend any more, the inner lining barrel 2 is rotated to a second station, the sample inlet 7 is blocked by the outer shell 1 of the reaction kettle, and then heating and roasting treatment is started.
In some embodiments, the inner wall of the outer shell 1 of the reaction kettle is a cylinder, the inner lining cylinder 2 is also a cylinder, and the inner lining cylinder 2 is rotatably and fittingly installed with the outer shell 1 of the reaction kettle. Two sample inlet holes 7 are formed in the side wall of the inner lining barrel 2, the two sample inlet holes 7 are vertically separated and correspondingly arranged, and two corresponding infusion holes 6 are formed in the side wall of the reaction kettle outer shell 1.
The slurry feeding mode is that a metering pump is used for pressurizing and conveying, as shown in fig. 1, a metering pump 5 sucks slurry from a slurry tank 4, then the slurry is respectively pumped into the lining cylinder 2 from two liquid conveying holes 6 on the side wall of the reaction kettle through a sample inlet hole 7, and simultaneously the slurry is also injected into the inner cavity of the lining cylinder 2 from the top of the reaction kettle in a spraying mode. The pumping speed of the slurry was 1 mL/min. When the liquid level of the slurry injected into the reaction kettle is slightly lower than the top surface of the carbon material three-dimensional grid 3, namely the slurry covers the carbon material three-dimensional grid 3, the lining cylinder 2 is rotated to a second station, so that the sample inlet hole 7 is blocked by the outer shell 1 of the reaction kettle, and then the heating and roasting treatment is started.
The outer shell 1 of the reaction kettle is made of metal material. The liner 2 is a carbon material. The carbon material three-dimensional grid 3 is formed by mutually connecting carbon fiber wires with the diameter of 10nm to form a network structure.
The spacing between adjacent carbon fiber filaments of the three-dimensional network 3 of carbon material is 500 nm.
The carbon material three-dimensional grid 3 is fixedly connected with the inner wall of the lining cylinder 2, and the carbon material three-dimensional grid 3 and the lining cylinder 2 can be arranged integrally or separately.
(4) After the slurry is filled, the lining cylinder 2 is rotated to a second station, and the communication state between the lining cylinder and the infusion hole 6 of the outer shell 1 of the reaction kettle is cut off. At the moment, the reaction kettle is placed in a tubular furnace to be roasted in nitrogen atmosphere, and the reaction kettle is roasted at the constant temperature of 500 ℃ for 12 hours.
(5) Taking out the sample from the reaction kettle, crushing, sieving with a 200-mesh sieve, uniformly mixing with 19.41g of sucrose, and roasting at 650 ℃ for 15 hours under the nitrogen atmosphere. Crushing the obtained sample, and sieving the crushed sample with a 200-mesh sieve to obtain LiMn with the average primary particle size of 1 mu m and regular pore channels in crystals0.3Fe0.7PO4And (3) active components of the positive electrode material.
Example 2
The embodiment provides a preparation method of a lithium battery positive electrode material, which comprises the following steps:
(1) 148.68g of Li were weighed2CO3、224.93g Fe2O3、600g(NH4)3PO4、104.96gMnO2Dissolving in solution containing citric acid, mixing, and preparing LiMn by liquid phase method0.3Fe0.7PO4And (3) precursor.
(2) Mixing LiMn0.3Fe0.7PO4Precursor additionIn water, the proportion of the precursor to the water is as follows: the amount of water is 150% of the mass of the precursor, then 25.89g of sucrose is added and mixed evenly, and the mixture is sanded and sieved by a 3000-mesh sieve to obtain filtrate, namely the slurry.
(3) The filtrate was pumped from the upper, middle and lower parts of the reaction vessel by a metering pump at a rate of 1mL/min, the reaction vessel used was the same as that of example 1, and the carbon material three-dimensional mesh 3 was formed by connecting carbon fiber filaments having a diameter of 3nm to each other, thereby forming a network structure.
(4) After the slurry is filled, the lining barrel 2 is rotated to a second station, and the communication state between the lining barrel 2 and the infusion hole 6 of the outer shell 1 of the reaction kettle is cut off. At this time, the reaction kettle was placed in a tube furnace under nitrogen atmosphere and kept at 600 ℃ for 20 hours. Taking out the sample from the reaction kettle, and crushing and sieving the sample by a 200-mesh sieve to obtain LiMn with the average primary particle size of 1 mu m and regular pore channels in crystals0.3Fe0.7PO4And (3) active components of the positive electrode material.
Example 3
The embodiment provides a preparation method of a lithium battery positive electrode material, which comprises the following steps:
(1) 727.51g of Li were taken2CO3、1493.66g Fe2O3、4000g(NH4)3PO4、85.60gMnO2Dissolving in solution containing citric acid, mixing, and preparing LiMn by liquid phase method0.05Fe0.95PO4And (3) precursor.
(2) Mixing LiMn0.05Fe0.95PO4Adding the precursor into water, wherein the ratio of the precursor to the water is as follows: the amount of water is 100% of the mass of the precursor, 75.68g of glucose is added and mixed evenly, the mixture is sanded and sieved by a 2500-mesh sieve, and the obtained filtrate is the slurry.
(3) The filtrate was pumped from the upper, middle and lower parts of the reaction vessel by a metering pump at a rate of 1mL/min, the reaction vessel used was the same as that of example 1, and the carbon material three-dimensional mesh 3 was formed by mutually connecting carbon fiber filaments having a diameter of 5nm, thereby forming a network structure.
(4) After the slurry is filled, the lining cylinder 2 is rotated to a second station, and the communication state between the lining cylinder and the infusion hole 6 of the outer shell 1 of the reaction kettle is cut off. At this time, the reaction kettle is placed in the tubeThe temperature of the furnace is kept constant at 700 ℃ for 16h under the nitrogen atmosphere. Taking out the sample from the reaction kettle, and crushing and sieving the sample by a 200-mesh sieve to obtain LiMn with the average primary particle size of 2 mu m and regular pore channels in crystals0.05Fe0.95PO4And (3) positive electrode material active components.
The XRD characterization of the prepared cathode material is shown in figure 3, and the characteristic peak of the cathode material is matched with that of a standard card, has an olivine structure and has no impurity phase peak. The TEM representation is shown in FIG. 4, and the regular channel structure in the crystal can be seen.
Example 4
This example provides a method for preparing a positive electrode material for a lithium battery, which is different from example 1 only in that the carbon material for preparing the three-dimensional carbon grid 3 in step (3) is acidified to be hydrophilic.
Wherein, the acidification treatment step comprises: taking a carbon raw material for preparing the carbon material three-dimensional grid 3, putting the carbon raw material and concentrated nitric acid (the mass percentage concentration is 68%) in a three-necked bottle according to a solid-to-liquid ratio of 1:10, carrying out oil bath at 60 ℃, refluxing and stirring for 6h, filtering, washing the carbon raw material with deionized water for multiple times until the carbon raw material is neutral, and drying at 60 ℃ to obtain the hydrophilic carbon raw material. The 1C discharge performance of the cathode material prepared in this example was better than that of the material prepared in example 1, and the results are shown in table 1. The carbon fiber filaments of the carbon material three-dimensional grid 3 are provided with hydrophilic functional groups which can be more easily formed into attachment points for forming crystal nuclei, crystals grow around the carbon fiber filaments, a pore canal penetrating through the center of the crystals is left in the crystals through a subsequent roasting process, and lithium ions which are difficult to migrate in the center of the crystals can more easily migrate outwards. The designed range of the spacing between the hydrophilic carbon fiber filaments is wider.
Example 5
This example provides a method for preparing a positive electrode material for a lithium battery, which is different from example 2 only in that the carbon material for preparing the carbon material three-dimensional grid 3 in step (3) is acidified and has hydrophilicity.
Wherein, the acidification treatment step comprises: taking a carbon raw material for preparing the carbon material three-dimensional grid 3, putting the carbon raw material and concentrated nitric acid (the mass percentage concentration is 68%) in a three-necked bottle according to a solid-to-liquid ratio of 1:10, carrying out oil bath at 60 ℃, refluxing and stirring for 6h, filtering, washing the carbon raw material with deionized water for multiple times until the carbon raw material is neutral, and drying at 60 ℃ to obtain the hydrophilic carbon raw material.
Comparative example 1
The comparative example provides a preparation method of a lithium battery positive electrode material, which comprises the following steps:
(1) 727.51g of Li were taken2CO3、1493.66g Fe2O3、4000g(NH4)3PO4、85.60gMnO2Dissolving in solution containing citric acid, mixing, and preparing LiMn by liquid phase method0.05Fe0.95PO4And (3) precursor.
(2) Mixing LiMn0.05Fe0.95PO4Adding the precursor into water, wherein the ratio of the precursor to the water is as follows: the amount of water is 100% of the mass of the precursor, 75.68g of glucose is added and mixed evenly, the mixture is sanded and sieved by a 2500-mesh sieve, and the obtained filtrate is the slurry.
(3) And (3) putting the filtrate into a conventional high-pressure reaction kettle, putting the high-pressure reaction kettle into a tubular furnace in a state that a reaction kettle cover is removed, heating the high-pressure reaction kettle to 700 ℃ in a nitrogen atmosphere, and keeping the temperature for 16 hours. Taking out the sample from the reaction kettle, and crushing and sieving the sample by a 200-mesh sieve to obtain LiMn0.05Fe0.95PO4And (3) active components of the positive electrode material.
The XRD characterization map of the cathode material is shown in figure 3, and the characteristic peak is consistent with a standard card, is of an olivine structure and has no impurity phase peak. The TEM representation of the crystal is shown in FIG. 5, and no regular channel structure appears in the crystal.
The cathode materials obtained in examples 1 to 5 and comparative example 1 above were examined, and the average primary particle diameter and pore size are shown in table 1.
TABLE 1
Average primary particle diameter Size of pore canal
Example 1 1μm 9.70nm
Example 2 1μm 3.20nm
Example 3 2μm 5.50nm
Example 4 1μm 9.20nm
Example 5 1μm 2.80nm
Comparative example 1 2μm -
Application example 1
The application example provides a button type lithium ion battery and tests the electrochemical performance of the button type lithium ion battery. The positive active components of the button lithium ion battery respectively adopt the positive active components of the positive materials prepared in the embodiment 3 and the comparative example 1, and the specific preparation method of the button lithium ion battery comprises the following steps:
800g of LiMn from example 3 were taken0.05Fe0.95PO4Active ingredient of positive electrode material, 100g conductive agent acetyleneAdding 100g of binder polyvinylidene fluoride (PVDF) into 800g of N-methylpyrrolidone solution (NMP solution), and stirring for 2 hours in a vacuum stirrer to prepare anode slurry; and uniformly coating the positive electrode slurry on an aluminum foil, then placing the aluminum foil in a vacuum drying oven for drying at 120 ℃ for 12h, and punching the aluminum foil into a circular sheet with the diameter of 14mm after rolling to obtain the positive electrode sheet. A positive plate, a negative plate (a metal lithium plate with the diameter of 14.5 mm), a diaphragm (Celgard 2400 microporous polypropylene film) and an electrolyte (1mo1/L LiPF)6the/EC + DMC (1: 1 by volume)) was assembled in a hydrogen-filled glove box into a CR2025 button lithium ion battery.
800g of LiMn from example 1 were taken0.3Fe0.7PO4And assembling the active components of the cathode material into the CR2025 button lithium ion battery by the method.
800g of the active component of the positive electrode material obtained in example 4 was assembled into a CR2025 button lithium ion battery by the same method as above.
800g of LiMn from comparative example 1 were taken0.05Fe0.95PO4Adding an active ingredient of a positive electrode material, 100g of conductive agent acetylene black and 100g of binder polyvinylidene fluoride (PVDF) into 800g of N-methylpyrrolidone solution (NMP solution), and stirring for 2 hours in a vacuum stirrer to prepare positive electrode slurry; the slurry is uniformly coated on an aluminum foil, then the aluminum foil is placed in a vacuum drying oven for drying at 120 ℃ for 12h, and after rolling, the aluminum foil is punched into a wafer with the diameter of 14mm to be used as a positive plate. A positive plate, a negative plate (a metal lithium plate with the diameter of 14.5 mm), a diaphragm (Celgard 2400 microporous polypropylene film) and an electrolyte (1mo1/L LiPF)6the/EC + DMC (1: 1 by volume)) was assembled in a hydrogen-filled glove box to form a CR2025 button lithium ion cell as a comparative cell.
And (3) charge and discharge test: the prepared test battery in application example 1 was subjected to a charge and discharge test by a lithium ion battery charge and discharge test system at-20 ℃, and the charge and discharge conditions were as follows: the charging termination voltage is 3.75V; the discharge termination voltage is 2.00V; charge-discharge current density: 0.2C and 1C. The characterization maps of the coin cells made of the positive electrode materials of examples 1, 3 and 4 and the coin cell made of the positive electrode material of comparative example 1 are shown in fig. 6.
Wherein, the discharge capacity of the button cell 1C made of the anode material in the embodiment 3 is 95.6mAh/g, the discharge capacity of the button cell 1C made of the anode material in the embodiment 1 is 96.0mAh/g, and the discharge capacity of the button cell 1C made of the anode material in the embodiment 4 is 96.6 mAh/g. Comparative example 1 the button cell 1C made of the positive electrode material had a discharge capacity of 57.3 mAh/g.
From the discharge capacity results shown in fig. 6 and above, it can be known that the long-range ordered pore structure is constructed in the anode material crystal, so that the lithium ion and electron transfer speed can be greatly increased, the impedance is reduced, and the low-temperature performance is improved.
The results of measuring the active ingredients of the positive electrode materials obtained in examples 1 and 4 are shown in table 2.
TABLE 2
Average primary particle diameter Total pore volume -20 ℃ and 1C discharge
Example 1 1μm 0.028cm3/g 96.0mAh/g
Example 4 1μm 0.029cm3/g 96.6mAh/g
The carbon material for preparing the carbon material three-dimensional grid 3 in the example 1 is not subjected to the acidification treatment, but the carbon material is subjected to the acidification treatment in the example 4, and as can be seen from the table 2, the pore channel effect of the example 4 subjected to the acidification surface treatment is better, so that the low-temperature performance is also better.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. The lithium battery positive electrode material is characterized in that a plurality of long-range orderly through-communicated pore channels are formed in the positive electrode material; preferably, the pore diameter of the pore channel is 3-50 nm, and/or the pore channel interval of the pore channel is 20-500 nm.
2. The positive electrode material for a lithium battery as claimed in claim 1, wherein the positive electrode material for a lithium battery is a phosphate-based positive electrode material.
3. The method for preparing a positive electrode material for a lithium battery as claimed in claim 1 or 2, wherein the positive electrode material is prepared by using a reaction vessel having a three-dimensional grid of a carbon material; preferably, the reaction kettle with the carbon material three-dimensional grid comprises an outer shell, a lining barrel is arranged in the outer shell, the lining barrel is internally provided with the three-dimensional grid formed by interweaving a plurality of carbon fiber yarns, and the periphery of the three-dimensional grid is connected with the inner wall of the lining barrel; further preferably, the diameter of the carbon fiber filaments is 3-50 nm, and/or the space between adjacent carbon fiber filaments in the same grid layer of the three-dimensional grid is 20-500 nm, and the space between adjacent grid layers is 20-500 nm.
4. The method according to claim 3, wherein the carbon fiber yarn raw material is acidified by a strong oxidizing acid, preferably nitric acid or concentrated sulfuric acid.
5. The method for preparing according to claim 3 or 4, characterized in that it comprises the steps of: and filling the slurry of the precursor of the positive electrode material into the reaction kettle with the carbon material three-dimensional grid, and then roasting in an inert atmosphere or an oxygen-free atmosphere to obtain the positive electrode material of the lithium battery.
6. The preparation method according to claim 5, wherein the outer shell is rotatably fitted with the lining cylinder, a sample inlet is formed in a side wall of the lining cylinder, a transfusion hole is correspondingly fitted in the outer shell of the reaction kettle, and a first station for communicating and fitting the sample inlet with the transfusion hole and a second station for plugging the sample inlet by the outer shell of the reaction kettle are provided during rotation of the lining cylinder;
preferably, the filling of the slurry of the precursor of the cathode material into the reaction kettle with the three-dimensional grid of the carbon material comprises: rotating the lining cylinder to a first station, injecting the slurry into the reaction kettle from the side part of the reaction kettle through the infusion hole and the sample inlet hole in sequence, rotating the lining cylinder to a second station after the liquid level in the reaction kettle reaches a set height, and finishing slurry filling;
further preferably, the slurry in the reaction kettle is injected into the reaction kettle from the side part of the reaction kettle, and simultaneously, the slurry is injected into the reaction kettle from the top part of the reaction kettle.
7. The preparation method according to claim 5 or 6, wherein the roasting temperature is 300-700 ℃; and/or the roasting time is 8-20 h.
8. The preparation method according to any one of claims 5 to 7, wherein the proportion of the positive electrode material precursor to water in the slurry of the positive electrode material precursor is as follows: the using amount of water is 60-200% of the mass of the anode material precursor; preferably, the slurry is prepared by mixing the positive electrode material precursor with water, sanding and sieving, and preferably, the sieved sieve is more than or equal to 2000 meshes.
9. The method for preparing according to claim 5, characterized in that the method for preparing comprises the steps of:
filling slurry of a precursor of the anode material into the reaction kettle with the carbon material three-dimensional grid;
roasting the reaction kettle in an inert atmosphere;
taking out the roasted product from the reaction kettle, mixing the roasted product with a carbon source, and then roasting for the second time to obtain the lithium battery anode material;
preferably, the roasting temperature is 300-500 ℃ under inert atmosphere;
alternatively, the preparation method comprises the steps of:
filling the slurry of the precursor of the anode material mixed with the carbon source into the reaction kettle with the carbon material grid;
roasting the reaction kettle in an inert atmosphere;
taking out the roasted product from the reaction kettle to obtain the lithium battery anode material;
preferably, the roasting temperature is 500-700 ℃ under inert atmosphere;
further preferably, the carbon source is any one or a mixture of glucose, sucrose, PVDF, carbon black, PEG, and paraffin.
10. A lithium battery positive electrode material produced by the production method according to any one of claims 3 to 9.
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CN108172794A (en) * 2017-12-27 2018-06-15 中科廊坊过程工程研究院 A kind of composite positive pole and its preparation method and application
CN109524658A (en) * 2018-12-06 2019-03-26 深圳市德方纳米科技股份有限公司 Anode material for lithium-ion batteries and preparation method thereof and lithium ion battery

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CN101453006A (en) * 2007-12-03 2009-06-10 中国科学院成都有机化学有限公司 Lithium ionic cell electrode material with micro hole construction and manufacturing method thereof
CN101941685A (en) * 2009-07-09 2011-01-12 河南新飞科隆电源有限公司 Preparation of spherical lithium iron phosphate material and lithium ion battery using spherical lithium iron phosphate material
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