CN113871602B - P-Cu negative electrode material for lithium ion battery - Google Patents
P-Cu negative electrode material for lithium ion battery Download PDFInfo
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- CN113871602B CN113871602B CN202111151855.0A CN202111151855A CN113871602B CN 113871602 B CN113871602 B CN 113871602B CN 202111151855 A CN202111151855 A CN 202111151855A CN 113871602 B CN113871602 B CN 113871602B
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a phosphorus-copper negative electrode material for a lithium ion battery, which comprises phosphorus, nanoscale copper particles and an outer cladding layer, wherein a layer of resin is coated outside the phosphorus, the nanoscale copper particles are adhered to the surface of the resin, the phosphorus and the nanoscale copper particles are wrapped by the outer cladding layer, and the outer cladding layer consists of a layer of citric acid cracking carbon and a layer of asphalt cracking carbon. The invention effectively reduces the activity of phosphorus, greatly improves the safety of the later preparation process, provides a bonding effect for the landing and fixing of nano copper particles on the surface of phosphorus, and greatly improves the conductivity of phosphorus.
Description
Technical Field
The invention relates to a novel lithium ion battery negative electrode material, in particular to a phosphorus copper negative electrode material for a lithium ion battery.
Background
The current commercial lithium ion battery anode material is a graphite carbon anode material, the capacity of the current commercial lithium ion battery anode material is close to the theoretical specific capacity (372 mAh/g), the capacity of the lithium ion battery is further improved to face a bottleneck problem, and the development requirement of a miniaturized electronic product cannot be met. The theoretical specific capacity of the phosphide cathode material reaches 2596mAh/g (the specific capacity of the first discharge of the material sample exceeds 10000 mAh/g). However, phosphorus basically has no conductivity, is unfavorable for lithium ion transport in the interior of the phosphorus, has strong phosphorus activity, is unfavorable for synthesis and development of the phosphorus, and cannot be commercialized until now.
The current synthesis technology of phosphorus-based alloy is mainly that phosphorus powder and metal powder are ball milled or react at high temperature. Because the activity of the phosphorus is stronger, the treatment condition is more severe, the treatment efficiency is low and the potential safety hazard is large. The prepared alloy has the problems of incomplete reaction, non-uniformity and the like, so that the obtained phosphorus-based alloy sample shows poor capacity exertion and cycle performance.
In addition, the possible volume effects of phosphorus-based alloys cannot be suppressed, nor is it possible to increase the cycling stability to obtain commercial materials, in the absence of subsequent treatments.
Disclosure of Invention
The invention aims to provide a phosphorus-copper negative electrode material for a lithium ion battery, which can effectively improve the capacity and energy density of the battery and overcome the defects of the prior art.
The technical scheme for solving the technical problems is as follows: the phosphorus-copper negative electrode material for the lithium ion battery comprises phosphorus, nanoscale copper particles and an outer cladding layer, wherein a layer of epoxy resin is coated outside the phosphorus, the nanoscale copper particles are adhered to the surface of the resin, the phosphorus and the nanoscale copper particles are wrapped by the outer cladding layer, and the outer cladding layer consists of a layer of citric acid cracking carbon and a layer of asphalt cracking carbon; the sum of the masses of the citric acid cracking carbon and the asphalt cracking carbon accounts for 10% -30% of the total mass of the material; the atomic ratio of the phosphorus to the copper is 1:1, or 1:2, or 1:3, or 2:1;
the phosphorus copper cathode material for the lithium ion battery is prepared through the following steps:
s1) phosphorus in mass ratio: resin=85:15, phosphorus powder and resin are weighed and ball-milled for 5 hours under the protection of argon atmosphere;
s2) putting the phosphorus-resin mixture into a sodium borohydride aqueous solution, slowly dripping a copper chloride aqueous solution into the sodium borohydride solution through a titrator, and rapidly stirring, wherein the mass of the sodium borohydride and the mass of the copper chloride are weighed according to the reaction molar ratio, and the excess of the sodium borohydride is 5%;
s3) filtering the obtained semi-finished product, and then putting the semi-finished product into deionized water for fully stirring, cleaning and filtering;
s4) placing the powder into a vacuum drying box for vacuum drying for 24 hours to obtain phosphor copper powder;
s5) weighing the phosphor copper powder and the citric acid according to the proportion, fully dissolving the citric acid by using deionized water, introducing the phosphor copper powder, and performing ball milling for 5 hours;
s6) heating the mixture under the protection of nitrogen atmosphere by spray drying, preserving the temperature of 460 ℃ for 4 hours and 600 ℃ for 6 hours, and naturally cooling to normal temperature;
s7) grinding and sieving with a 200-mesh sieve, weighing asphalt, ball milling for 5 hours, spray drying, heating under the protection of nitrogen atmosphere, preserving heat for 4 hours at the temperature of 500 ℃ in a curve, preserving heat for 6 hours at the temperature of 900 ℃, and naturally cooling to normal temperature;
s8) grinding and sieving with a 200-sieve to obtain a final finished product;
wherein S3) is repeated twice.
The beneficial effects of the invention are as follows:
1. the coating resin can effectively reduce the activity of phosphorus, greatly improve the safety of the later preparation process, provide a bonding effect for the landing and fixing of nano copper particles on the surface of phosphorus, and greatly improve the conductivity of phosphorus.
2. The shell covers the volume expansion headspace where phosphorus may be present.
3. The outer cladding shell layer has certain hardness, thoroughly solves the problem of dissolution of phosphorus in electrolyte, controls the lithium intercalation reaction and volume expansion of phosphorus in a core-shell structure, and can effectively improve the cycle life and stability of the cathode material.
In addition, the method is simple and convenient to prepare, low in cost, beneficial to large-scale production and beneficial to realizing commercialization of the novel phosphorus-based anode material.
Drawings
Fig. 1 is a schematic structural view of a phosphor-copper anode material for a lithium ion battery according to the present invention.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.
As shown in fig. 1, the invention provides a phosphor-copper negative electrode material for a lithium ion battery, which comprises phosphor coated with resin, nano-scale copper particles and an outer coating layer, wherein the phosphor is externally coated with a layer of resin, such as epoxy resin and phenolic resin, so that the activity of the phosphor is thoroughly reduced, and the mass ratio of the resin is as follows: phosphorus=15:85; the nano-scale copper particles are adhered on the surface of the resin, so that the conductivity of the material is enhanced; the outer part of the phosphor copper particle is an outer coating layer, the outer coating layer is composed of a layer of citric acid cracking carbon and a layer of asphalt cracking carbon, the cracking carbon accounts for 10% -30% of the total mass of the material, and further, the citric acid cracking carbon and the asphalt cracking carbon account for half of the total mass of the material.
The atomic ratio of phosphor copper is P: cu=1:1, or P: cu=1:2, or P: cu=1:3, or P: cu=2:1.
The following table forms a plurality of examples of the phosphor-copper anode material of the present invention and the corresponding specific capacity for initial discharge and specific capacity for discharge after 100 cycles.
The preparation method of the phosphorus copper anode material comprises the following steps:
1. phosphorus in mass ratio: resin=85:15, phosphorus powder and resin are weighed and ball-milled for 5 hours under the protection of argon atmosphere;
2. putting the phosphorus-resin mixture into sodium borohydride aqueous solution, slowly dripping copper chloride aqueous solution into the sodium borohydride solution through a titrator, and rapidly stirring, wherein the mass of sodium borohydride and copper chloride is weighed according to the reaction molar ratio, and the excess of sodium borohydride is 5%;
3. after the full reaction, filtering the obtained semi-finished product, then putting deionized water into the semi-finished product for full stirring, cleaning and filtering, and repeating the steps twice;
4. vacuum drying in a vacuum drying oven for 24 hours to obtain phosphorus copper powder;
5. weighing phosphorus copper powder (70% -90%) and citric acid (5% -15%) according to a proportion, fully dissolving the citric acid by using deionized water, introducing the phosphorus copper powder, and performing ball milling for 5 hours;
6. spray drying the mixture, heating under nitrogen atmosphere, keeping the temperature curve at 460 ℃ for 4 hours, keeping the temperature at 600 ℃ for 6 hours, and naturally cooling to normal temperature;
7. grinding, sieving with 200 mesh sieve, weighing asphalt (5% -15%), ball milling for 5 hr, spray drying, heating under nitrogen atmosphere protection, maintaining temperature at 500 deg.C for 4 hr, maintaining temperature at 900 deg.C for 6 hr, and naturally cooling to normal temperature;
8. grinding and sieving with 200 sieves to obtain the final product.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents, and modifications which are not to be construed as being within the scope of the invention.
Claims (1)
1. The phosphorus copper negative electrode material for the lithium ion battery is characterized by comprising phosphorus, nanoscale copper particles and an outer cladding layer, wherein the outer part of the phosphorus is coated with a layer of epoxy resin, the nanoscale copper particles are adhered to the surface of the resin, the outer cladding layer wraps the phosphorus and the nanoscale copper particles, and the outer cladding layer consists of a layer of citric acid cracking carbon and a layer of asphalt cracking carbon; the sum of the masses of the citric acid cracking carbon and the asphalt cracking carbon accounts for 10% -30% of the total mass of the material; the atomic ratio of the phosphorus to the copper is 1:1, or 1:2, or 1:3, or 2:1;
the phosphorus copper cathode material for the lithium ion battery is prepared through the following steps:
s1) phosphorus in mass ratio: resin=85:15, phosphorus powder and resin are weighed and ball-milled for 5 hours under the protection of argon atmosphere;
s2) putting the phosphorus-resin mixture into a sodium borohydride aqueous solution, slowly dripping a copper chloride aqueous solution into the sodium borohydride solution through a titrator, and rapidly stirring, wherein the mass of the sodium borohydride and the mass of the copper chloride are weighed according to the reaction molar ratio, and the excess of the sodium borohydride is 5%;
s3) filtering the obtained semi-finished product, and then putting the semi-finished product into deionized water for fully stirring, cleaning and filtering;
s4) placing the powder into a vacuum drying box for vacuum drying for 24 hours to obtain phosphor copper powder;
s5) weighing the phosphor copper powder and the citric acid according to the proportion, fully dissolving the citric acid by using deionized water, introducing the phosphor copper powder, and performing ball milling for 5 hours;
s6) heating the mixture under the protection of nitrogen atmosphere by spray drying, preserving the temperature of 460 ℃ for 4 hours and 600 ℃ for 6 hours, and naturally cooling to normal temperature;
s7) grinding and sieving with a 200-mesh sieve, weighing asphalt, ball milling for 5 hours, spray drying, heating under the protection of nitrogen atmosphere, preserving heat for 4 hours at the temperature of 500 ℃ in a curve, preserving heat for 6 hours at the temperature of 900 ℃, and naturally cooling to normal temperature;
s8) grinding and sieving with a 200-sieve to obtain a final finished product;
wherein S3) is repeated twice.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202111151855.0A CN113871602B (en) | 2018-07-18 | 2018-07-18 | P-Cu negative electrode material for lithium ion battery |
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| CN202111151855.0A CN113871602B (en) | 2018-07-18 | 2018-07-18 | P-Cu negative electrode material for lithium ion battery |
| CN201810793764.9A CN108987707B (en) | 2018-07-18 | 2018-07-18 | Phosphorus-copper negative electrode material for lithium ion battery and preparation method thereof |
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| CN113871602B true CN113871602B (en) | 2023-06-20 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104701500A (en) * | 2013-12-06 | 2015-06-10 | 奇瑞汽车股份有限公司 | Preparation method of lithium ion battery composite cathode material, cathode material and battery |
| CN105826533A (en) * | 2016-03-28 | 2016-08-03 | 顺德职业技术学院 | Silicon-carbon composite for lithium ion battery and preparation method of silicon-carbon composite |
| CN107492651A (en) * | 2017-09-05 | 2017-12-19 | 中国科学院物理研究所 | A kind of nano-silicon negative material of double-coating and its preparation method and application |
| CN107681126A (en) * | 2016-08-02 | 2018-02-09 | 清华大学 | Phosphorus carbon composite, the battery of its preparation method and application the phosphorus carbon composite |
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| CN101286559A (en) * | 2007-04-13 | 2008-10-15 | 财团法人工业技术研究院 | Composite material of phosphide and cathode material of lithium ion cell |
| CN106025194B (en) * | 2016-05-12 | 2019-04-02 | 安泰科技股份有限公司 | A kind of black phosphorus base composite negative pole material and preparation method thereof |
| CN106920953B (en) * | 2017-05-05 | 2019-05-24 | 顺德职业技术学院 | Lithium sulfur battery anode material and preparation method thereof with core-shell structure |
| CN107293725B (en) * | 2017-07-18 | 2020-07-28 | 深圳市泽纬科技有限公司 | Preparation method of nano red phosphorus and graphene composite negative electrode material |
| CN107634210B (en) * | 2017-09-22 | 2020-02-07 | 常州大学 | High-performance lithium/sodium battery negative electrode material and preparation method thereof |
| CN108232132B (en) * | 2017-12-13 | 2020-12-29 | 中国科学院福建物质结构研究所 | Battery cathode material and preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104701500A (en) * | 2013-12-06 | 2015-06-10 | 奇瑞汽车股份有限公司 | Preparation method of lithium ion battery composite cathode material, cathode material and battery |
| CN105826533A (en) * | 2016-03-28 | 2016-08-03 | 顺德职业技术学院 | Silicon-carbon composite for lithium ion battery and preparation method of silicon-carbon composite |
| CN107681126A (en) * | 2016-08-02 | 2018-02-09 | 清华大学 | Phosphorus carbon composite, the battery of its preparation method and application the phosphorus carbon composite |
| CN107492651A (en) * | 2017-09-05 | 2017-12-19 | 中国科学院物理研究所 | A kind of nano-silicon negative material of double-coating and its preparation method and application |
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| CN108987707B (en) | 2021-10-26 |
| CN113871602A (en) | 2021-12-31 |
| CN108987707A (en) | 2018-12-11 |
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