How to define a custom aggregation function to sum a column of Vectors?

Spark >= 3.0

You can use Summarizer with sum

import org.apache.spark.ml.stat.Summarizer

df
  .groupBy($"id")
  .agg(Summarizer.sum($"vec").alias("vec"))

Spark <= 3.0

Personally I wouldn't bother with UDAFs. There are more than verbose and not exactly fast (Spark UDAF with ArrayType as bufferSchema performance issues) Instead I would simply use reduceByKey / foldByKey:

import org.apache.spark.sql.Row
import breeze.linalg.{DenseVector => BDV}
import org.apache.spark.ml.linalg.{Vector, Vectors}

def dv(values: Double*): Vector = Vectors.dense(values.toArray)

val df = spark.createDataFrame(Seq(
    (1, dv(0,0,5)), (1, dv(4,0,1)), (1, dv(1,2,1)),
    (2, dv(7,5,0)), (2, dv(3,3,4)), 
    (3, dv(0,8,1)), (3, dv(0,0,1)), (3, dv(7,7,7)))
  ).toDF("id", "vec")

val aggregated = df
  .rdd
  .map{ case Row(k: Int, v: Vector) => (k, BDV(v.toDense.values)) }
  .foldByKey(BDV.zeros[Double](3))(_ += _)
  .mapValues(v => Vectors.dense(v.toArray))
  .toDF("id", "vec")

aggregated.show

// +---+--------------+
// | id|           vec|
// +---+--------------+
// |  1| [5.0,2.0,7.0]|
// |  2|[10.0,8.0,4.0]|
// |  3|[7.0,15.0,9.0]|
// +---+--------------+

And just for comparison a "simple" UDAF. Required imports:

import org.apache.spark.sql.expressions.{MutableAggregationBuffer,
  UserDefinedAggregateFunction}
import org.apache.spark.ml.linalg.{Vector, Vectors, SQLDataTypes}
import org.apache.spark.sql.types.{StructType, ArrayType, DoubleType}
import org.apache.spark.sql.Row
import scala.collection.mutable.WrappedArray

Class definition:

class VectorSum (n: Int) extends UserDefinedAggregateFunction {
    def inputSchema = new StructType().add("v", SQLDataTypes.VectorType)
    def bufferSchema = new StructType().add("buff", ArrayType(DoubleType))
    def dataType = SQLDataTypes.VectorType
    def deterministic = true 

    def initialize(buffer: MutableAggregationBuffer) = {
      buffer.update(0, Array.fill(n)(0.0))
    }

    def update(buffer: MutableAggregationBuffer, input: Row) = {
      if (!input.isNullAt(0)) {
        val buff = buffer.getAs[WrappedArray[Double]](0) 
        val v = input.getAs[Vector](0).toSparse
        for (i <- v.indices) {
          buff(i) += v(i)
        }
        buffer.update(0, buff)
      }
    }

    def merge(buffer1: MutableAggregationBuffer, buffer2: Row) = {
      val buff1 = buffer1.getAs[WrappedArray[Double]](0) 
      val buff2 = buffer2.getAs[WrappedArray[Double]](0) 
      for ((x, i) <- buff2.zipWithIndex) {
        buff1(i) += x
      }
      buffer1.update(0, buff1)
    }

    def evaluate(buffer: Row) =  Vectors.dense(
      buffer.getAs[Seq[Double]](0).toArray)
} 

And an example usage:

df.groupBy($"id").agg(new VectorSum(3)($"vec") alias "vec").show

// +---+--------------+
// | id|           vec|
// +---+--------------+
// |  1| [5.0,2.0,7.0]|
// |  2|[10.0,8.0,4.0]|
// |  3|[7.0,15.0,9.0]|
// +---+--------------+

See also: How to find mean of grouped Vector columns in Spark SQL?.