CN110380017B - N-type silicon material for high-capacity high-rate lithium ion battery cathode - Google Patents
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The invention discloses an n-type silicon material for a high-capacity high-rate lithium ion battery cathode, which comprises silicon and black phosphorus and is characterized in that: the active material layer contains silicon, the coating layer is black phosphorus, and the mass of the black phosphorus of the coating layer is not less than 2.2% of the mass of the silicon. According to the invention, the surface of the material is coated with phosphorus and silicon is doped with phosphorus, so that the contact between silicon and an electrolyte is isolated, the volume expansion of the material is limited, the conductivity is increased, the continuous growth of SEI and the consumption of active lithium are avoided, and the rate capability and the cycle performance of the silicon material are improved. Reasonable phosphorus content, slightly reduced theoretical gram capacity of the negative electrode, and finally high reversible capacity of silicon.
Description
Technical Field
The invention relates to a lithium ion battery, in particular to a negative electrode material of the lithium ion battery, and especially relates to a negative electrode n-type silicon material for a high-capacity high-rate lithium ion battery.
Background
The negative electrode of the lithium ion battery is obtained by mixing a negative electrode active material, a binder and an additive to prepare slurry, uniformly coating the slurry on two sides of a negative electrode current collector and drying the slurry. The commonly used negative active material is a carbon material, such as graphite, but due to the problem of low specific capacity, the application of the negative active material in a high-capacity high-rate lithium ion battery (such as a power lithium ion battery) is restricted.
The theoretical gram capacity of silicon is 4200mAh/g (Li) 4.4 Si) and graphite 372 mAh/g (LiC) 6 ) Silicon is the lithium ion battery negative electrode material with the highest specific capacity. But due to its large volume effect (>300%) and the silicon electrode material can be pulverized and peeled off from the current collector in the charging and discharging processes, so that the active material and the active material, and the active material and the current collector can not lose electric contact with each otherNew solid electrolyte layer SEI is formed, eventually leading to deterioration of electrochemical performance of the battery. In addition, pure silicon is a semiconductor material, and the rate performance is inferior to that of graphite due to very low intrinsic electronic conductivity, so that it is difficult to directly apply unmodified silicon to a lithium battery cathode. The Chinese patent application CN107093708A discloses a preparation method of an all-n-type silicon lithium ion battery cathode material, which comprises the steps of carrying out ball milling micron treatment and sand milling nano treatment on an n-type silicon material in sequence, cleaning the n-type silicon powder by using acetone and ultrapure water in sequence, carrying out surface oxidation treatment on the n-type silicon powder, mixing the oxidized silicon powder with a conductive agent and a binder to prepare cathode slurry, and preparing a cathode plate through coating, drying, tabletting and the like. The method treats the silicon to enable the silicon to be used for the negative electrode of the lithium battery, and simultaneously shows that n-type silicon has higher lithium storage capacity and rate capability than p-type silicon. But does not solve the problems caused by the volume effect. In addition, as the circulation progresses, the silicon material gradually concentrates towards the surface of the negative plate away from the current collector.
The theoretical gram capacity of phosphorus is close to 2600mAh/g (Li) 3 P) is 7 times that of graphite. The phosphorus is classified into white phosphorus, red phosphorus and black phosphorus, wherein the white phosphorus is toxic and has a low melting point, the red phosphorus is inflammable and slightly soluble in water, and the black phosphorus has good conductivity, the weakest reaction activity, the most stable property in the air and high density, so the black phosphorus is most suitable for the lithium ion battery. The unit cell of the black phosphorus is far larger than that of graphite, the distance between the formed lithium intercalation reaction channels is 0.43nm and is larger than 0.3354nm of the graphite, and the characteristic determines that lithium ions have high diffusion coefficient in the orthorhombic black phosphorus. Taking the phospholene material as an example, the diffusion rate of lithium ions therein is 100 to 10000 times faster than graphite. The electronic conductivity of the black phosphorus is up to 10 2 S/m is not less than 10 of graphite 1 ~10 3 And (5) S/m. In addition, since the lithium intercalation potential of phosphorus is 0.8V, which is higher than that of silicon, the density of phosphorus is 2.69g/cm 3 Higher than 2.33 g/cm for silicon 3 Therefore, the black phosphorus is very suitable for the lithium battery negative electrode material. However, phosphorus has a volume effect as silicon, and the lithium intercalation potential of phosphorus is too high, which results in a lower battery voltage, so that pure phosphorus is not optimal as a negative electrode material.
In the prior art, phosphorus is usually applied by doping, for example, chinese patent application CN107240693A discloses a phosphorus-doped silicon-graphite composite material, which contains phosphorus-doped n-type silicon and graphite. During preparation, a mixture I containing silicon and phosphorus is subjected to ball milling in a protective gas atmosphere to obtain a precursor, and a mixture II containing the precursor and graphite powder is subjected to ball milling in the protective gas atmosphere to obtain the phosphorus-doped silicon-graphite composite material. For another example, chinese patent application CN107482173A discloses a negative active material of a lithium ion battery, which comprises a composite formed by connecting a carbon material and black phosphorus through a C — P bond. According to the technical scheme, the negative electrode material is obtained through doping, the problem of volume expansion can be restrained to a certain extent, the problem of volume expansion still exists, and the phenomenon that the silicon material slowly moves to the surface of the negative electrode plate in the battery circulation process cannot be solved.
Disclosure of Invention
The invention aims to provide an n-type silicon material for a high-capacity high-rate lithium ion battery cathode, which limits the volume expansion of the silicon material, increases the conductivity and is suitable for a high-capacity high-rate lithium ion battery.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: the n-type silicon material for the negative electrode of the high-capacity high-magnification lithium ion battery comprises silicon and black phosphorus and consists of an internal active material layer and an external coating layer, wherein the active material layer contains silicon, the coating layer is black phosphorus, and the mass of the black phosphorus of the coating layer is not less than 2.2% of the mass of the silicon.
In the above technical solution, the inner active material layer contains one or more of black phosphorus, carbon, and silicon monoxide in addition to silicon.
Preferably, the total mass of the black phosphorus in the active material layer and the coating layer is 2.2-22% of the mass of silicon.
The theoretical gram capacity of silicon in the fully lithium-intercalated state is 4200mAh/g (Li) 4.4 Si), the theoretical gram capacity of phosphorus is 2596mAh/g (Li) 3 P). When a lithium ion battery is first formed, most of the lithium salt is consumed to form a negative solid electrolyte interface film SEI. Lithium is an acceptor material, and a coating layer is applied on the surface of the silicon negative electrodePhosphorus can enable the formed SEI film to have electric neutrality, and meanwhile, strong bonds between the phosphorus and silicon can tend to be alloyed, so that the influence of an electric field on carriers in a silicon body is effectively weakened.
Si is a tetravalent element, Li is a monovalent element, and P is a pentavalent element, so 1 mole of Li 4.4 With 0.4 mol of lithium in Si, 1 mol of Li, possibly forming acceptor impurities 3 Also 2 moles of lithium are required in P to form a neutral species. The current optimal first coulombic efficiency for silicon based materials is 90%, so 10% of silicon is considered for the first loss under the limiting conditions. The amount n of phosphorus species required for the outer coating p Amount n of substance being silicon si 0.1 x 0.4/2=0.02 times. Since the atomic weight of phosphorus is 31 and the atomic weight of silicon is 28, the lower limit mass of phosphorus coated on the silicon surface is 0.02/28 × 31=2.2% of the silicon mass. When silicon is used in the negative electrode of a lithium ion battery in a state where a complete lithium intercalation occurs, the state is Li 4.4 Si, so the amount n of phosphorus species required p Amount n of substance being silicon si 0.4/2=0.2 times. Since the atomic weight of phosphorus is 31 and the atomic weight of silicon is 28, the upper limit mass of phosphorus coated on the silicon surface is 0.2/28 × 31=22% of the silicon mass.
Besides the black phosphorus in the coating layer, other black phosphorus is doped with silicon in the active material layer by thermal diffusion, implantation or mixing.
In the above technical solution, the inner active material layer includes one or more of a nano silicon material, a porous silicon material, a hollow silicon material, a silicon-carbon composite material, and a silicon-oxygen composite material. Wherein the inner active material layer may be doped with black phosphorus.
In the technical scheme, the silicon surface is coated with the black phosphorus, so that the contact between the silicon and the electrolyte is isolated, and the continuous growth of an SEI (solid electrolyte interface film) and the consumption of active lithium are avoided. Meanwhile, the coated black phosphorus tends to have the structural characteristics of phospholene, so that the volume expansion of silicon can be limited to a certain extent. The contact internal resistance among active material particles can be reduced by utilizing the high conductivity characteristic of the black phosphorus on the surface, and the multiplying power of the battery is improved. It is worth noting that the black phosphorus of the coating layer can solve the phenomenon that the silicon material slowly moves to the surface of the negative plate in the battery cycle process.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. according to the invention, the surface of the material is coated with phosphorus, so that the contact between silicon and electrolyte is isolated, the black phosphorus of the coating tends to have the structural characteristics of phospholene, the volume change of silicon can be inhibited, the contact between silicon and electrode liquid can be effectively isolated, and the continuous growth of SEI and the consumption of active lithium are avoided.
2. In the invention, the black phosphorus on the surface has high conductivity, so that the contact internal resistance among active material particles can be reduced; the doped phosphorus in the silicon enables the silicon to form an n-type electronic conductive semiconductor, improves the conductivity of the silicon material, has high diffusion performance, and finally improves the rate capability of the silicon material.
3. According to the invention, through the arrangement of the coating layer, the phenomenon that the silicon material slowly moves to the surface of the negative plate in the battery circulation process can be solved, and the circulation performance of the silicon material is greatly improved finally.
4. The invention provides reasonable phosphorus content, slightly reduces the theoretical gram capacity of the cathode, and finally leads the silicon to have high reversible capacity.
5. Compared with the traditional graphite cathode, the invention has the characteristic of high capacity; compared with a pure silicon negative electrode, the invention has the characteristics of high multiplying power and long cycle life.
Drawings
Fig. 1 is a cell test cycle scenario of an embodiment of the present invention;
fig. 2 is a result of the cell normal temperature 2C rate charge test of the embodiment.
Detailed Description
The invention is further described below with reference to the following examples:
the first embodiment is as follows:
the preparation method of the n-type silicon material for the negative electrode of the high-capacity high-rate lithium ion battery comprises the following steps:
mixing the negative active material with a conductive agent and a binder to prepare slurry, uniformly coating the slurry on two sides of a negative current collector to form an active material layer, and drying and compacting to obtain the negative plate.
The negative active material mainly comprises a silicon material and a graphite material, wherein the mass of black phosphorus in the silicon material is 10% of the mass of silicon. Black phosphorus forms bulk phase doping of silicon by means of thermal diffusion or ion implantation and forms a very small amount of coating with surface residue, coating layers of the rest main bodies form a coating layer on the main silicon surface by a vapor deposition method, a spraying method, a hydrothermal method or a sol-gel method, and the mass of black phosphorus of the coating layer is 2.2% of that of a silicon material.
The negative plate prepared by the method is matched with a 622 ternary positive plate to assemble a 50Ah square aluminum shell monomer cell, and the energy density is up to 250Wh/kg (the model of the square cell: 2614891).
And (3) testing the cycle conditions (the cycle step is that 1C constant current charging is carried out to 4.2V, constant voltage charging is carried out to 0.05C, standing is carried out for 0.5h, 1C constant current discharging is carried out to 2.7V, and standing is carried out for 0.5 h) under the condition of 25 +/-2 ℃, as shown in figure 1, the cycle life of the ordinary n-type silicon material battery cell is 1000 times, the cycle life of the n-type silicon material battery cell doped with 10% of phosphorus can reach 1500-1600 times, and the cycle life is improved by 50% compared with the ordinary n-type silicon material battery cell.
The normal temperature 2℃ rate charging test (test procedure: 2℃ constant current charging to 4.2V at 25 ± 2 ℃ and constant voltage charging to 0.05C) was carried out, and the results are shown in fig. 2, in which the constant current charging ratio of the ordinary n-type silicon material cell was 87.25%, while the temperature rise was 12.3 ℃, while the constant current charging ratio of the 10% phosphorus-doped n-type silicon material cell was 88.81%, and the temperature rise was only 7.7 ℃. A higher constant current charge ratio means less polarization of the cell, and a lower temperature rise means less heat generation. In conclusion, the cell performance of the n-type silicon material doped with 10% of phosphorus is superior to that of the cell of the common n-type silicon material.
Example two:
mixing silicon with different phosphorus contents, graphite, a conductive agent and a binder, and coating to prepare the pole piece, wherein the mass of the phosphorus-containing silicon accounts for 10% of the weight of all solids, the mass of the graphite accounts for 85%, and the mass of the conductive agent and the binder of the other auxiliary materials accounts for 5%. The density of the coated double-sided surface is 220g/m 2 The pole piece compaction density is 1.7g/cm3, the size of the negative pole piece is 80 x 143mm, the number of the negative pole pieces is 80, and the same 622 ternary system positive pole piece is matched to test the normal-temperature 1C charge-discharge cycle life and 2C constant-current charge of the battery under the same conditionsThe in ratio and the 2C charge temperature rise, the test results are given in the table below.
From the results of the comparative groups, the 1 st group and the 5 th group and the results of the 2 nd, the 3 rd and the 6 th groups, along with the increase of the content of doped phosphorus, the cycle life, the constant current charging ratio and the temperature rise of the battery are improved compared with the phosphorus-free comparative group, such as the cycle life is increased, the constant current charging ratio is improved, and the temperature rise is reduced. Comparing the results of groups 1 and 2, the results of groups 3 and 4, and the results of groups 5 and 6, the test results for the coated layer were better than the uncoated layer at the same phosphorus content.
Claims (4)
1. An n-type silicon material for a high-capacity high-magnification lithium ion battery cathode comprises silicon and black phosphorus, and is characterized in that: the active material layer contains silicon, the coating layer is black phosphorus, the mass of the black phosphorus of the coating layer is not less than 2.2% of the mass of the silicon, the inner active material layer contains the black phosphorus besides the silicon, and the black phosphorus forms bulk phase doping of the silicon by means of thermal diffusion or ion implantation or a mixed mode of the two and forms a coating with a small amount of surface residues.
2. The n-type silicon material for the negative electrode of the high-capacity high-rate lithium ion battery according to claim 1, wherein: the total mass of the black phosphorus in the active material layer and the doping layer is 2.2-22% of the mass of silicon.
3. The n-type silicon material for the negative electrode of the high-capacity high-rate lithium ion battery according to claim 1, wherein: the inner active material layer comprises one or more of nano silicon material, porous silicon material, hollow silicon material, silicon-carbon composite material and silicon-oxygen composite material.
4. The n-type silicon material for the negative electrode of the high-capacity high-rate lithium ion battery according to claim 3, wherein: and black phosphorus is doped in the active material layer at the inner part.
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| CN110911173B (en) * | 2019-12-05 | 2021-10-12 | 苏州易得能新能源科技有限公司 | Ultrafast-charging high-capacity phosphorus alkene composite activated carbon material |
| CN112670468B (en) * | 2020-11-27 | 2022-04-26 | 宁德晟硕科技有限公司 | Lithium ion battery and preparation process thereof |
| CN112803014B (en) * | 2021-01-28 | 2022-05-06 | 合肥国轩高科动力能源有限公司 | N-type high-conductivity Si-based negative electrode material and preparation method thereof |
| CN114784251A (en) * | 2022-05-13 | 2022-07-22 | 中国科学技术大学 | Phosphorus-coated negative electrode material and preparation method and application thereof |
| CN115020687B (en) * | 2022-08-08 | 2022-11-18 | 深圳市华宝新能源股份有限公司 | Positive electrode material and preparation method and application thereof |
| CN117012942B (en) * | 2023-09-28 | 2024-03-15 | 江苏正力新能电池技术有限公司 | Silicon-graphite composite negative plate, preparation method thereof and lithium ion battery |
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